Thiol compound derivative, curable composition containing the derivative, and molded product thereof

ABSTRACT

The present invention relates to a thiol compound derivative represented by the following formula (1), a curable composition containing the derivative, and a molded product made of the composition. More particularly, the invention relates to a thiol compound derivative which is added to a polymer having reactivity to a thiol derivative substituent to provide a curable composition, a curable composition containing the derivative and a crosslinkable halogen-containing crosslinking polymer, and a crosslinked molded product of the composition.  
                 
 
wherein X 1 , X 2  and X 3  are each a group represented by the following formula (2).

TECHNICAL FIELD

The present invention relates to a thiol compound derivative, a curablecomposition containing the derivative, and a molded product made of thecomposition. More particularly, the invention relates to a thiolcompound derivative which is added to a polymer having reactivity to athiol derivative substituent to provide a curable composition, a curablecomposition containing the derivative and a crosslinkablehalogen-containing crosslinking polymer, and a crosslinked moldedproduct of the composition.

BACKGROUND ART

Epichlorohydrin rubber, chlorine-containing acrylic rubber, etc. havebeen heretofore widely used for molded articles, such as hoses andsealing parts, because they are excellent in various properties, such asoil resistance, heat resistance, weathering resistance, ozone resistanceand compression set.

In general, halogen-containing crosslinking polymers, such as theepichlorohydrin rubber and the chlorine-containing acrylic rubber, areoften stored in the form of compositions obtained by adding crosslinkingadditives, such as crosslinking agent and crosslinking accelerator, tothe polymers.

When diene type rubber compositions or chlorine type rubber compositionscontaining vulcanizing additives, such as vulcanizing agent andvulcanization accelerator, are stored, vulcanization generally proceedsslowly, and as a result, changes, e.g., increase of viscosity, reductionof scorch time and decrease of vulcanizing rate, are brought about tothereby lower processability of the compositions into molded articles orproperties of the vulcanization products. From the viewpoint ofretention of storage stability, these changes are desired to be small.If the vulcanization additives are not added, these changes are small.From the viewpoint of productivity, however, curable compositions inwhich the vulcanization additives are added in advance are generallyemployed, and therefore, it becomes important to improve storagestability of the compositions containing the vulcanization additives.

As the vulcanization additives for the diene type rubbers or thechlorine type rubbers, polythiol compounds, such as dithiol compoundsand trithiol compounds, are conventionally known.

These polythiol compounds, however, have high reactivity, so that whenthe rubbers and the vulcanization additives are kneaded and processed,premature vulcanization sometimes takes place, or even if kneading canbe carried out smoothly without premature vulcanization, gelationsometimes takes place during the subsequent storing stage. Thus, thecompositions have a problem of lack of storage stability even if theproperties of the resulting cured products are excellent.

As the crosslinking additives for the halogen-containing crosslinkingpolymers, triazinethiols are known.

The triazinethiols, however, have high reactivity and high crosslinkingrate, so that when the rubbers and the crosslinking additives arekneaded and processed, premature crosslinking sometimes takes place, oreven if kneading can be carried out smoothly without prematurecrosslinking, gelation sometimes takes place to increase viscosity inthe subsequent storing stage, or partial crosslinking is promoted. Thatis to say, scorching is liable to occur, and hence, molding troubles aresometimes brought about.

On this account, an attempt to use a premature vulcanization inhibitorin combination to improve storage stability has been made. By the use ofthe premature vulcanization inhibitor in combination, however, problemsof decrease of vulcanizing rate and deterioration of heat resistance arebrought about.

For controlling the crosslinking rate, there has been also made anattempt to add metal oxide, metal hydroxide, carbonate, organic acidsalt or the like and to select the type of metal, type of counter ion,etc. according to the reactivity of the halogen-containing crosslinkingpolymers and the reactivity of the triazinethiols. However, ifsatisfactory crosslinking rate is intended to be obtained, the scorchtime is sometimes shortened.

Accordingly, there has been desired development of a novel thiolcompound derivative capable of providing a rubber composition or a resincomposition having excellent storage stability, processability andcurability without using a premature vulcanization inhibitor that exertsevil influences on the properties of a cured product of a diene typerubber composition, a chlorine type rubber (halogen-containingcrosslinking polymer) composition or the like. There has been alsodesired development of a curable composition having storage stabilityand moderate crosslinking rate and capable of providing a crosslinkedproduct having excellent physical properties with a good balance.

The present inventors have earnestly studied to solve such problems asmentioned above, and as a result, they have found that by the use of, asa crosslinking agent, a thiol compound derivative wherein a thiolcompound is protected by a protective group of vinyl ether or the like,a curable composition having excellent storage stability andcrosslinking rate and capable of providing a crosslinked product ofexcellent physical properties can be obtained without using a prematurevulcanization inhibitor that exerts evil influences on the properties ofa cured product of a halogen-containing crosslinking polymer compositionor a diene type rubber composition. Based on the finding, the presentinvention has been accomplished.

It is an object of the present invention to provide a novel thiolcompound derivative capable of providing a rubber composition or a resincomposition having excellent storage stability, processability andcurability. It is another object of the invention to provide a curablecomposition comprising a halogen-containing crosslinking polymer andhaving a good balance of storage stability, crosslinking rate andphysical properties of its crosslinked product. It is a further objectof the invention to provide a molded product of the curable composition.

DISCLOSURE OF THE INVENTION

The thiol compound derivative of the present invention is a thiolcompound derivative represented by the following formula (1):

wherein X¹, X² and X³ may be the same or different and are each a grouprepresented by the following formula (2):

wherein A is an oxygen atom or a sulfur atom,

R¹ is a hydrogen atom, an alkyl group or a phenyl group,

R² is a group selected from the group consisting of the following groups(a) to (f),

R³ is a hydrogen atom, an alkyl group or a phenyl group, and

R¹ and R² may form a ring;

(a) a group selected from an alkyl group, a halogenated alkyl group, analkyl group having at least one hydroxyl group, an alkenyl group, analkynyl group and an aralkyl group,

(b) a residue wherein a hydroxyl group is removed from a hydroxylgroup-containing compound selected from alkylene glycol, dialkyleneglycol, trialkylene glycol, tetraalkylene glycol, allyl alcohols,ketooximes, alkanolamines, dialkanolamines, trialkanolamines,trialkylsilanol, alicyclic alcohol and naphthyl alcohols,

(c) a group represented by the following formula (3):—CHY—CH₂X  (3)wherein X is any one of a halogen atom, an alkoxy group, an alkoxyalkoxygroup, a dialkylamino group, a trialkylsilyl group, an acetoxy group anda piperidino group, and Y is a hydrogen atom or a halogen atom,

(d) a group represented by the following formula (4):

wherein Z is any one of a hydrogen atom, a halogen atom, a nitro group,an amino group, an alkoxy group, an alkylamino group, a dialkylaminogroup, an alkyl group and an acyl group, and n is an integer of 1 to 3and is a number of substituents Z bonded to the phenyl group skeleton inthe formula (4),

(e) a group represented by —CH₂—C₆H₅ or —CHCH₃—C₆H₅, and

(f) a group represented by the following formula (5) or (6):

wherein R¹ and R³ are the same as R¹ and R³ in the formula (2), A is anoxygen atom or a sulfur atom, and R⁴ is any one of —CH₂—, —CH₂CH₂—,—CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —CH₂CH₂OCH₂CH₂—, —CH₂CH₂OCH₂CH₂OCH₂CH₂—,

In the above thiol compound derivative, it is preferable that in theformula (2), A is an oxygen atom, R¹ is a hydrogen atom, R² is an alkylgroup or a residue wherein a hydroxyl group is removed from(poly)alkylene glycol, and R³ is a hydrogen atom.

The formula (2) is preferably represented by the following formula (7):

wherein n is 3 or 4.

The thiol compound derivative of the present invention is a thiolcompound derivative represented by the following formula (8):

wherein X¹ and X² may be the same or different and are each a grouprepresented by the following formula (2):

said formula (2) being the same as that previously described.

The thiol compound derivative of the present invention is a thiolcompound derivative represented by the following formula (9):

wherein X¹ and X² may be the same or different and are each a grouprepresented by the following formula (2), and M is an alkali metal or analkaline earth metal;

said formula (2) being the same as that previously described.

The thiol compound derivative of the present invention is a thiolcompound derivative represented by the following formula (10):

wherein X¹ and X² may be the same or different and are each a grouprepresented by the following formula (2), and R⁵ is a group selectedfrom the following groups (g) to (k);

said formula (2) being the same as that previously described;

(g) a group selected from a hydrogen atom, an alkyl group, an alkenylgroup, an alkynyl group, a phenyl group, an aralkyl group and —NH₂,

(h) a dialkylamino group represented by the following formula (11):—NR⁶R⁷  (11)wherein R⁶ and R⁷ are each a group selected from an alkyl group, analkenyl group, an alkynyl group, an aralkyl group, a benzyl group, anallyl group, a cycloalkyl group, a fluoroalkyl group and a phenyl group,and R⁶ and R⁷ may be the same or different,

(i) a monoalkylamino group represented by the following formula (12):—NHR⁸  (12)wherein R⁸ is a group selected from an alkyl group, an alkenyl group, analkynyl group, an aralkyl group, a benzyl group, an allyl group, acycloalkyl group, a fluoroalkyl group, an anilino group, ahydroxyanilino group and a phenyl group,

(j) a group represented by the following formula (13):—OR⁹  (13)wherein R⁹ is a group selected from an alkyl group, an alkenyl group, anaralkyl group, a halogenophenyl group, a naphthyl group, a cycloalkylgroup and a phenyl group, and

(k) a group represented by the following formula (14):—SR¹⁰  (14)wherein R¹⁰ is a group selected from an alkyl group, an alkenyl group,an alkynyl group, a phenyl group, an aralkyl group, a halogenophenylgroup, a naphthyl group and a cycloalkyl group.

In the above thiol compound derivative, it is preferable that in theformula (2), A is an oxygen atom, R¹ is a hydrogen atom, R² is an alkylgroup or a residue wherein a hydroxyl group is removed from(poly)alkylene glycol, and R³ is a hydrogen atom.

In the above thiol compound derivative, it is also preferable that theformula (2) is represented by the following formula (7):

wherein n is 3 or 4.

The thiol compound derivative of the present invention is a thiolcompound derivative represented by the following formula (15):

wherein X¹ is a group represented by the following formula (2), and R⁵is the same as R⁵ in the formula (10);

said formula (2) being the same as that previously described.

The thiol compound derivative of the present invention is a thiolcompound derivative represented by the following formula (16):

wherein X¹ is a group represented by the following formula (2), M is analkali metal or an alkaline earth metal, and R⁵ is the same as R⁵ in theformula (10);

said formula (2) being the same as that previously described.

The curable composition of the present invention contains any one of theabove-mentioned thiol compound derivatives of the present invention.

The curable composition of the present invention contains:

a halogen-containing crosslinking polymer, and

a thiol compound derivative having, in one molecule, at least onefunctional group represented by the following formula (17):

wherein A, R¹, R² and R³ are the same as A, R¹, R² and R³ in the formula(2).

The functional group represented by the formula (17) is preferablyformed by reacting a compound having a thiol group (—SH) with a vinylether.

In the above curable composition, the thiol compound derivative ispreferably a compound represented by the following formula (1):

wherein X¹, X² and X³ are each a group represented by the followingformula (2):

said formulas (1) and (2) being the same as those previously described.

In the above curable composition, the thiol compound derivative is alsopreferably a compound represented by the following formula (8):

wherein X¹ and X² may be the same or different and are each a grouprepresented by the following formula (2):

said formula (2) being the same as that previously described.

In the above curable composition, the thiol compound derivative is alsopreferably a compound represented by the following formula (9):

wherein X¹ and X² are each a group represented by the following formula(2):

said formulas (9) and (2) being the same as those previously described.

In the above curable composition, the thiol compound derivative is alsopreferably a compound represented by the following formula (10):

wherein X¹ and X² are each a group represented by the following formula(2):

said formulas (10) and (2) being the same as those previously described.

In the above curable composition, the thiol compound derivative is alsopreferably a compound represented by the following formula (15):

wherein X¹ is a group represented by the following formula (2):

said formulas (15) and (2) being the same as those previously described.

In the above curable composition, the thiol compound derivative is alsopreferably a compound represented by the following formula (16):

wherein X¹ is a group represented by the following formula (2):

said formulas (16) and (2) being the same as those previously described.

In the curable compositions of the invention, it is preferable that inthe formulas (2) and (17), A is an oxygen atom, R¹ is a hydrogen atom,R² is an alkyl group or a residue wherein a hydroxyl group is removedfrom (poly)alkylene glycol, and R³ is a hydrogen atom.

The formulas (2) and (17) are each preferably represented by thefollowing formula (7):

wherein n is 3 or 4.

The curable composition of the present invention contains a compoundobtained by contacting triazinethiol with a polyvalent vinyl ether, anda halogen-containing crosslinking polymer.

The triazinethiol is preferably represented by the following formula(18):

The triazinethiol is also preferably represented by the followingformula (19):

wherein R⁵ is the same as R⁵ in the formula (10).

The polyvalent vinyl ether is preferably at least one ether selectedfrom divinyl ethers, trivinyl ethers and tetravinyl ethers.

In the curable compositions of the present invention, thehalogen-containing crosslinking polymer is preferably an acrylic rubber,an epichlorohydrin rubber, a chloroprene rubber or chlorosulfonatedpolyethylene.

The curable compositions of the present invention preferably contain anorganic acid metal salt, and the organic acid metal salt is preferablyan organic acid alkali metal salt and/or an organic acid alkaline earthmetal salt. The curable compositions of the present invention preferablyfurther contain, in addition to the organic acid metal salt, avulcanization supplement accelerator, and the vulcanization supplementaccelerator is preferably an onium salt and/or polyalkylene oxide.

The curable compositions of the present invention preferably contain anamine type anti-aging agent, and a sulfur compound or a phosphoruscompound.

The molded product of the present invention is obtained by crosslinkingthe curable composition of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chart of an IR absorption spectrum of a synthetic substanceobtained in Example 1.

FIG. 2 is a chart of an IR absorption spectrum of1,3,5-triazine-2,4,6-trithiol that is a starting material for synthesis.

FIG. 3 is a chart of an IR absorption spectrum of a sample obtained byheating the synthetic substance obtained in Example 1, in theatmosphere.

FIG. 4 is a chart of an IR absorption spectrum of a synthetic substanceobtained in Example 2.

FIG. 5 is a chart of an IR absorption spectrum of a sample obtained byheating the synthetic substance obtained in Example 2, in theatmosphere.

FIG. 6 shows curelastometer curves of Examples 3 to 7 and ComparativeExamples 2, 4 and 5.

Numeral 1 in FIG. 6 designates a curelastometer curve of Example 3.

Numeral 2 in FIG. 6 designates a curelastometer curve of Example 4.

Numeral 3 in FIG. 6 designates a curelastometer curve of Example 5.

Numeral 4 in FIG. 6 designates a curelastometer curve of Example 6.

Numeral 5 in FIG. 6 designates a curelastometer curve of Example 7.

Numeral 6 in FIG. 6 designates a curelastometer curve of ComparativeExample 2.

Numeral 7 in FIG. 6 designates a curelastometer curve of ComparativeExample 4.

Numeral 8 in FIG. 6 designates a curelastometer curve of ComparativeExample 5.

FIG. 7 is a chart of an IR absorption spectrum of a synthetic substanceobtained in Example 34.

FIG. 8 is a chart of an IR absorption spectrum of a synthetic substanceobtained in Example 35.

FIG. 9 is a chart of an IR absorption spectrum of6-dibutylamino-S-triazine-2,4-dithiol that is a starting material forsynthesis.

FIG. 10 is a chart of an IR absorption spectrum of a synthetic substanceobtained in Example 36.

FIG. 11 is a chart of an IR absorption spectrum of a synthetic substanceobtained in Example 37.

FIG. 12 is a chart of an IR absorption spectrum of a synthetic substanceobtained in Example 38.

FIG. 13 is a chart of an IR absorption spectrum of a synthetic substanceobtained in Example 39.

FIG. 14 is a chart of an IR absorption spectrum of a sample obtained bystoring the synthetic substance obtained in Example 39, in theatmosphere.

FIG. 15 is a chart of an IR absorption spectrum of a synthetic substanceobtained in Example 40.

FIG. 16 is a chart of an IR absorption spectrum of a sample obtained bystoring the synthetic substance obtained in Example 40, in theatmosphere.

FIG. 17 is a chart of an IR absorption spectrum of a synthetic substanceobtained in Example 41.

FIG. 18 is a chart of an IR absorption spectrum of a sample obtained bystoring the synthetic substance obtained in Example 41, in theatmosphere.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is described in detail hereinafter.

Thiol Compound Derivative

The thiol compound derivative according to the invention is a derivativeof 1,3,5-triaziene-2,4,6-trithiol, 1,3,5-triazine-2,4-dithiol or thelike, and is a compound derivative wherein a hydrogen atom of a thiolgroup (—SH) of such a compound is replaced with a specific substituent.The thiol compound derivative can be obtained by reacting a thiolcompound such as triazinethiol with a vinyl ether. Examples of the thiolcompound derivatives are described below.

Trithiol Compound Derivative

The thiol compound derivative of the invention is, for example, a thiolcompound derivative represented by the following formula (1), which is aderivative of a trithiol compound.

In the formula (1), X¹, X² and X³ are each a group represented by thefollowing formula (2).

In the formula (1), X¹, X² and X³ may be the same or different,preferably the same.

In the formula (2), A is an oxygen atom or a sulfur atom.

R¹ is a hydrogen atom, an alkyl group or a phenyl group. R¹ ispreferably a hydrogen atom or an alkyl group, more preferably a hydrogenatom.

R² is a group selected from the group consisting of the following groups(a) to (f). In the present invention, a group selected from the groups(a) to (e) is preferable.

(a) A group selected from an alkyl group, a halogenated alkyl group, analkyl group having at least one hydroxyl group, an alkenyl group, analkynyl group and an aralkyl group. Of these, preferable is an alkylgroup or an alkenyl group.

The alkyl group is preferably an alkyl group of 1 to 25 carbon atoms,more preferably an alkyl group of 1 to 18 carbon atoms. The alkyl groupmay be any of straight-chain, branched and cyclic alkyl groups. Examplesof such alkyl groups include methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl,2-ethylhexyl, decyl, cetyl, stearyl and 1-menthyl. Of these, methyl,ethyl and n-propyl are preferable.

The halogenated alkyl group is, for example, a group wherein at leastone hydrogen atom of the above alkyl group is replaced with halogen.Examples of the halogen atoms include a fluorine atom, a chlorine atom,a bromine atom and an iodine atom. Of these, a fluorine atom ispreferable. Examples of the halogenated alkyl groups containing afluorine atom include a perfluoroalkyl group wherein all hydrogen atomsof the above alkyl group are replaced with fluorine atoms, and afluoroalkyl group represented by RfCH₂CH₂—. The Rf is, for example,perfluoromethyl, perfluoroethyl, perfluoropropyl or perfluorobutyl.

The alkyl group having one or more hydroxyl groups is, for example, agroup wherein at least one hydrogen atom of the above alkyl group isreplaced with a hydroxyl group. The alkyl group having one or morehydroxyl groups is preferably a group having one or two hydroxyl groups,more preferably a group having one hydroxyl group. The hydroxyl groupmay be any of primary, secondary and tertiary. Examples of the alkylgroups having such a hydroxyl group include alkyl groups having aprimary hydroxyl group, such as 2-hydroxyethyl, 3-hydroxypropyl and4-hydroxy-n-butyl, alkyl groups having a secondary hydroxyl group, suchas 1-hydroxyethyl, 2-hydroxypropyl and 3-hydroxy-n-butyl, and alkylgroups having a tertiary hydroxyl group, such as3-hydroxy-3-methyl-n-butyl.

The alkenyl group is preferably an alkenyl group of 1 to 20 carbonatoms, more preferably an alkenyl group of 1 to 10 carbon atoms.Examples of such alkenyl groups include propanedienyl, isopropenyl,3-methyl-2-butenyl, allyl and 2-methylallyl. Of these, isopropenyl andallyl are preferable.

The alkynyl group is preferably an alkynyl group of 1 to 20 carbonatoms, more preferably an alkynyl group of 1 to 10 carbon atoms.Examples of such alkynyl groups include propargyl and 1-phenylpropargyl.Of these, propargyl is preferable.

The aralkyl group is preferably an aralkyl group of 1 to 20 carbonatoms, more preferably an aralkyl group of 1 to 10 carbon atoms.Examples of such aralkyl groups include 4-phenylbutyl and methylbenzyl.Of these, methylbenzyl is preferable.

(b) A residue wherein a hydroxyl group is removed from a hydroxylgroup-containing compound selected from alkylene glycol, dialkyleneglycol, trialkylene glycol, tetraalkylene glycol, allyl alcohols,ketooximes, trialkanolamines, dialkanolamines, alkanolamines,trialkylsilanol, alicyclic alcohol and naphthyl alcohols. Of these,polyalkylene glycols, such as dialkylene glycol, trialkylene glycol andtetraalkylene glycol, are preferable.

Examples of the glycols, such as dialkylene glycol, trialkylene glycoland tetraalkylene glycol, include ethylene glycol, propylene glycol,butylene glycol, diethylene glycol, dipropylene glycol, dibutyleneglycol, diethylene glycol monobutyl ether, triethylene glycol,tripropylene glycol, tributylene glycol, tetraethylene glycol,tetrapropylene glycol and tetrabutylene glycol. Of these, ethyleneglycol is preferable.

Examples of the ketooximes include acetone ketooxime and methyl ethylketone ketooxime.

Examples of the trialkanolamines include triethanolamine andtripropanolamine.

Examples of the dialkanolamines include diethanolamine anddipropanolamine.

Examples of the monoalkanolamines include 4-dimethylaminobutanol and3-dimethylaminopropanol.

Examples of the trialkylsilanols include trimethylsilyl alcohol andtriethylsilyl alcohol.

Examples of the alicyclic alcohols include cyclohexyl alcohol andmenthol.

Examples of the naphthyl alcohols include naphthyl alcohol.

(c) A group represented by the following formula (3):—CHY—CH₂X  (3)wherein X is a halogen atom, an alkoxy group, an alkoxyalkoxy group, adialkylamino group, a trialkylsilyl group, an acetoxy group, apiperidino group or the like, and Y is a hydrogen atom or a halogenatom.

X is preferably a halogen atom, an alkoxy group or a dialkylamino group.

Examples of the groups represented by the formula (3) include1-chloroethyl, 2-chloroethyl, 1-bromoethyl, 2-bromoethyl, methoxyethyl,2-butoxyethyl, methoxyethoxyethyl, dimethylaminoethyl,2-(diethylamino)ethyl, aminoethyl, trimethylsilylethyl,trimethylsiloxyethyl, 2-acetoxyethyl and 2-piperidinoethyl. Of these,2-chloroethyl and methoxyethyl are particularly preferable.

(d) A group represented by the following formula (4):

wherein n is an integer of 1 to 3, preferably 1, and is a number ofsubstituents Z bonded to the phenyl group skeleton.

In the formula (4), Z is a hydrogen atom, a halogen atom, a nitro group,an amino group, an alkoxy group, an alkylamino group, a dialkylaminogroup, an alkyl group, an acyl group or the like.

Examples of the groups represented by the formula (4) include phenyl,methoxyphenyl, tolyl such as o-tolyl, isopropylphenyl, p-nitrophenyl,2-nitrophenyl, 3-nitrophenyl, fluorophenyl such as p-fluorophenyl,methoxyphenyl such as p-methoxyphenyl, aminophenyl such asp-aminophenyl, N-methylaminophenyl, p-(dimethylamino)phenyl,4-acetylphenyl, iodophenyl such as p-iodophenyl, chlorophenyl such asp-chlorophenyl, bromophenyl such as p-bromophenyl,2,4,6-trichlorophenyl, 2,4,6-trimethylphenyl, 2,4,6-tribromophenyl,2,4-dichlorophenyl, 2,4-dibromophehyl and 2,4-dimethylphenyl. Of these,phenyl and methoxyphenyl are preferable.

(e) A group represented by —CH₂—C₆H₅ or —CHCH₃—C₆H₅, namely,1-phenylethyl or benzyl.

(f) A group represented by the following formula (5) or (6):—R⁴-ACH═CH₂  (5)

In the formula (6), R¹ and R³ are the same as R¹ and R³ in the formula(2). In the formulas (5) and (6), A is an oxygen atom or a sulfur atom,and R⁴ is a divalent substituent, is any one of —CH₂—, —CH₂CH₂—,—CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —CH₂CH₂OCH₂CH₂—, —CH₂CH₂OCH₂CH₂OCH₂CH₂—,

Particularly preferable is a thiol compound derivative wherein in theformula (2), A is an oxygen atom, R¹ is a hydrogen atom, R² is an alkylgroup or a residue wherein a hydroxyl group is removed from(poly)alkylene glycol, and R³ is a hydrogen atom.

In the thiol compound derivative of the invention, R¹ and R² in theformula (2) may form a ring. When R¹ and R² form a ring, R¹ and R² areeach preferably an alkyl group, and the alkyl group may have asubstituent.

In the above case, R³ is preferably a hydrogen atom, and the ring formedfrom R¹ and R² is preferably represented by the following formula (7):

wherein n is 3 or 4.

The above-mentioned cyclic structure part may have a substituent.

Another thiol compound derivative according to the present invention isa thiol compound derivative represented by the following formula (8):

wherein X¹ and X² are each a group represented by the following formula(2):

In the formula (8), X¹ and X² may be the same or different, preferablythe same. The formula (2) is the same as that previously described.

Another thiol compound derivative according to the present invention isa thiol compound derivative represented by the following formula (9):

wherein X¹ and X² are each a group represented by the following formula(2):

In the formula (9), X¹ and X² may be the same or different, preferablythe same, and M is an alkali metal or an alkaline earth metal. Thealkali metal is preferably sodium or potassium, more preferably sodium.The alkaline earth metal is preferably calcium, magnesium or barium. Ofthese, sodium is preferable. The formula (2) is the same as thatpreviously described.

Examples of the thiol compound derivatives represented by the formula(1) (sometimes referred to as “derivative a” hereinafter) wherein X¹, X²and X³ are the same and X¹ is represented by the following formula (2)include thiol compound derivatives shown in the following Table 1(Tables 1-1 to 1-4). (1)

(2) Thiol compound derivative Derivative A R³ R¹ R² Tables 1-1 a1 a O HH methyl group a2 a O H H ethyl group a3 a O H H n-propyl group a4 a O HH isopropyl group a5 a O H H butyl group a6 a O H H isobutyl group a7 aO H H sec-butyl group a8 a O H H tert-butyl group a9 a O H H pentylgroup a10 a O H H hexyl group a11 a O H H heptyl group a12 a O H H octylgroup a13 a O H H 2-ethylhexyl group a14 a O H H decyl group a15 a O H Hcetyl group a16 a O H H stearyl group a17 a O H H 1-menthyl group a18 aO H H propanedienyl group a19 a O H H isopropenyl group a20 a O H H3-butynyl group a21 a O H H 3-methyl-2-butenyl a22 a O H H allyl groupa23 a O H H 2-methylallyl group a24 a O H H propargyl group a25 a O H H3-phenylpropargyl a26 a O H H residue wherein one hydroxyl group ofethylene glycol is removed a27 a O H H residue wherein one hydroxylgroup of propylene glycol is removed a28 a O H H residue wherein onehydroxyl group of butylene glycol is removed a29 a O H H residue whereinone hydroxyl group of diethylene glycol is removed a30 a O H H residuewherein one hydroxyl group of dipropylene glycol is removed a31 a O H Hresidue wherein one hydroxyl group of dibutylene glycol is removed a32 aO H H residue wherein one hydroxyl group of diethylene glycolmonobutylether is removed a33 a O H H residue wherein one hydroxyl groupof triethylene glycol is removed a34 a O H H residue wherein onehydroxyl group of tripropylene glycol is removed a35 a O H H residuewherein one hydroxyl group of tributylene glycol is removed Tables 1-2a36 a O H H residue wherein one hydroxyl group of tetraethylene glycolis removed a37 a O H H residue wherein one hydroxyl group oftetrapropylene glycol is removed a38 a O H H residue wherein onehydroxyl group of tetrabutylene glycol is removed a39 a O H H residuewherein one hydroxyl group of acetone oxime group is removed a40 a O H Hresidue wherein one hydroxyl group of triethanolamine is removed a41 a OH H residue wherein one hydroxyl group of diethanolamine is removed a42a O H H residue wherein one hydroxyl group of dimethylaminoethanol isremoved a43 a O H H residue wherein one hydroxyl group of trimethylsilylalcohol is removed a44 a O H H residue wherein one hydroxyl group oftriethylsilyl alcohol is removed a45 a O H H residue wherein onehydroxyl group of cyclohexyl alcohol is removed a46 a O H H residuewherein one hydroxyl group of menthol is removed a47 a O H H residuewherein one hydroxyl group of naphthyl alcohol is removed a48 a O H H1-chloroethyl group a49 a O H H 2-chloroethyl group a50 a O H H1-bromoethyl group a51 a O H H 2-bromoethyl group a52 a O H Hethoxyethyl group a53 a O H H 2-butoxyethyl group a54 a O H Hethoxyethoxyethyl group a55 a O H H dimethylaminoethyl group a56 a O H H2-(diethylamino)ethyl group a56 a O H H 3-dimethylaminopropyl group a57a O H H aminoethyl group a58 a O H H trimethylsilylethyl group a59 a O HH trimethylsiloxyethyl group a60 a O H H 2-acetoxyethyl group a61 a O HH 2-piperidinoethyl group a62 a O H H phenyl group a63 a O H Hmethoxyphenyl group a64 a O H H o-tolyl group a65 a O H Ho-isopropylphenyl group a66 a O H H p-nitrophenyl group a67 a O H H2-nitrophenyl group a68 a O H H 3-nitrophenyl group a69 a O H Hp-fluorophenyl group a70 a O H H p-methoxyphenyl group Tables 1-3 a71 aO H H p-aminophenyl group a72 a O H H N-methylaminophenyl group a73 a OH H p-(dimethylamino)phenyl group a74 a O H H 4-acetylphenyl group a75 aO H H p-iodophenyl group a76 a O H H p-chlorophenyl group a77 a O H Hp-bromophenyl group a78 a O H H 2,4,6-trichlorophenyl group a79 a O H H2,4,6-tribromophenyl group a80 a O H H 2,4,6-trimethylphenyl group a81 aO H H 2,4-dichlorophenyl group a82 a O H H 2,4-dibromophenyl group a83 aO H H 2,4-dimethylphenyl group a84 a O H H —CH₂OCH═CH₂ a85 a O H H—CH₂CH₂OCH═CH₂ a86 a O H H —CH₂CH₂CH₂OCH═CH₂ a87 a O H H—CH₂CH₂CH₂CH₂OCH═CH₂ a88 a O H H —CH₂CH₂OCH₂CH₂OCH═CH₂ a89 a O H H—CH₂CH₂OCH₂CH₂OCH₂CH₂OCH═CH₂ a90 a O H H —CH₂CH₂N(CH₂CH₂OH)CH₂CH₂OCH═CH₂a91 a O H H —Ph—OCH═CH₂ a92 a O H H —Ph—N═N—Ph—OCH═CH₂ a93 a O H H—Ph—C(CH₃)₂—Ph—OCH═CH₂ a94 a O H H -cyclohexylene-OCH═CH₂ a95 a O H H1-phenylethyl group a96 a O H H benzyl group a97 a

a98 a

Tables 1-4 a99 a

a100 a

a101 a

a102 a S H H 3-(trimethylsilyl)propyl group a103 a S H H 2-hydroxyethylgroup a104 a S H H (N-morpholino)ethyl group a105 a S H H2-(N-β-hydroxyethyl)aminoethyl group a106 a S H H 2-aminoethyl groupa107 a S H H p-chlorophenyl group a108 a S H H phenyl group a109 a S H Hvinyl group a110 a O Me H methyl group a111 a O Me H ethyl group a112 aO Et H methyl group a113 a O Et H ethyl group a114 a O Ph— H methylgroup a115 a O Ph— H ethyl group

In Table 1, “—Ph—” denotes a divalent aromatic substituent representedby C₆H₄; “cyclohexylene” denotes a divalent substituent havingcyclohexylene skeleton represented by C₆H₁₀; “Ph—” denotes a monovalentaromatic substituent represented by C₆H₅; “Me” denotes a methyl

group; “Et” denotes an ethyl group; and(thiol compound derivative a97) denotes a substituent X¹ wherein A is anoxygen atom, substituents R¹ and R² form a ring, and R³ is a hydrogenatom. Each of the thiol compound derivatives a98 to a101 has the samemeaning as that of the thiol compound derivative a97.

Examples of the thiol compound derivatives represented by the formula(8) (sometimes referred to as “derivative b” hereinafter) wherein X¹ andX² are the same and X¹ is represented by the following formula (2)include thiol compound derivatives shown in the following Table 2(Tables 2-1 to 2-4). (8)

(2) Thiol compound derivative Derivative A R³ R¹ R² Tables 2-1 b1 b O HH methyl group b2 b O H H ethyl group b3 b O H H n-propyl group b4 b O HH isopropyl group b5 b O H H n-butyl group b6 b O H H isobutyl group b7b O H H sec-butyl group b8 b O H H tert-butyl group b9 b O H H pentylgroup b10 b O H H hexyl group b11 b O H H heptyl group b12 b O H H octylgroup b13 b O H H 2-ethylhexyl group b14 b O H H decyl group b15 b O H Hcetyl group b16 b O H H stearyl group b17 b O H H 1-menthyl group b18 bO H H propanedienyl group b19 b O H H isopropenyl group b20 b O H H3-butynyl group b21 b O H H 3-methyl-2-butenyl group b22 b O H H allylgroup b23 b O H H 2-methylallyl group b24 b O H H propargyl group b25 bO H H 3-phenylpropargyl group residue wherein one hydroxyl group of b26b O H H residue wherein one hydroxyl group of ethylene glycol is removedb27 b O H H residue wherein one hydroxyl group of propylene glycol isremoved b28 b O H H residue wherein one hydroxyl group of butyleneglycol is removed b29 b O H H residue wherein one hydroxyl group ofdiethylene glycol is removed b30 b O H H residue wherein one hydroxylgroup of dipropylene glycol is removed b31 b O H H residue wherein onehydroxyl group of dibutylene glycol is removed b32 b O H H residuewherein one hydroxyl group of diethylene glycol monobutyl ether isremoved b33 b O H H residue wherein one hydroxyl group of triethyleneglycol is removed b34 b O H H residue wherein one hydroxyl group oftripropylene glycol is removed b35 b O H H residue wherein one hydroxylgroup of tributylene glycol is removed Tables 2-2 b36 b O H H residuewherein one hydroxyl group of tetraethylene glycol is removed b37 b O HH residue wherein one hydroxyl group of tetrapropylene glycol is removedb38 b O H H residue wherein one hydroxyl group of tetrabutylene glycolis removed b39 b O H H residue wherein one hydroxyl group of oxime groupis removed b40 b O H H residue wherein one hydroxyl group oftriethanolamine is removed b41 b O H H residue wherein one hydroxylgroup of diethanolamine is removed b42 b O H H residue wherein onehydroxyl group of dimethylaminoethanol is removed b43 b O H H residuewherein one hydroxyl group of trimethylsilyl alcohol is removed b44 b OH H residue wherein one hydroxyl group of triethylsilyl alcohol isremoved b45 b O H H residue wherein one hydroxyl group of cyclohexylalcohol is removed b46 b O H H residue wherein one hydroxyl group ofmenthol is removed b47 b O H H residue wherein one hydroxyl group ofnaphthylalcohol is removed b48 b O H H 1-chloroethyl group b49 b O H H2-chloroethyl group b50 b O H H 1-bromoethyl group b51 b O H H2-bromoethyl group b52 b O H H methoxyethyl group b53 b O H H2-butoxyethyl group b54 b O H H methoxyethoxyethyl group b55 b O H Hdimethylaminoethyl group b56 b O H H 2-(diethylamino)ethyl group b56 b OH H 3-dimethylaminopropyl group b57 b O H H aminoethyl group b58 b O H Htrimethylsilylethyl group b59 b O H H trimethylsiloxyethyl group b60 b OH H 2-acetoxyethyl group b61 b O H H 2-piperidinoethyl group b62 b O H Hphenyl group b63 b O H H methoxyphenyl group b64 b O H H o-tolyl groupb65 b O H H o-isopropylphenyl group b66 b O H H p-nitrophenyl group b67b O H H 2-nitrophenyl group b68 b O H H 3-nitrophenyl group b69 b O H Hp-fluorophenyl group b70 b O H H p-methoxyphenyl group Tables 2-3 b71 bO H H p-aminophenyl group b72 b O H H N-methylaminophenyl group b73 b OH H p-(dimethylamino)phenyl group b74 b O H H 4-acetylphenyl group b75 bO H H p-iodophenyl group b76 b O H H p-chlorophenyl group b77 b O H Hp-bromophenyl group b78 b O H H 2,4,6-trichlorophenyl group b79 b O H H2,4,6-tribromophenyl group b80 b O H H 2,4,6-trimethylphenyl group b81 bO H H 2 4-dichloro henyl group b82 b O H H 2,4-dibromophenyl group b83 bO H H 2,4-dimethylphenyl group b84 b O H H —CH₂OCH═CH₂ b85 b O H H—CH₂CH₂OCH═CH₂ b86 b O H H —CH₂CH₂CH₂OCH═CH₂ b87 b O H H—CH₂CH₂CH₂CH₂OCH═CH₂ b88 b O H H —CH₂CH₂OCH₂CH₂OCH═CH₂ b89 b O H H—CH₂CH₂OCH₂CH₂OCH₂CH₂OCH═CH₂ b90 b O H H —CH₂CH₂N(CH₂CH₂OH)CH₂CH₂OCH═CH₂b91 b O H H —Ph—OCH═CH₂ b92 b O H H —Ph—N═N—Ph—OCH═CH₂ b93 b O H H—Ph—C(CH₃)₂—Ph—OCH═CH₂ b94 b O H H -cyclohexylene-OCH═CH₂ 595 b O H H1-phenylethyl group b96 b O H H benzyl group b97 b

b98 b

b99 b

Tables 2-4 b100 b

b101 b

b102 b S H H 3-(trimethylsilyl)propyl group b103 b S H H 2-hydroxyethylgroup b104 b S H H 2-(N-morpholino)ethyl group b105 b S H H2-(N-β-hydroxyethyl) aminoethyl group b106 b S H H 2-aminoethyl groupb107 b S H H p-chlorophenyl group b108 b S H H phenyl group b109 b S H Hvinyl group b110 b O Me H methyl group b111 b O Me H ethyl group b112 bO Et H methyl group b113 b O Et H ethyl group b114 b O Ph— H methylgroup b115 b O Ph— H ethyl group

Examples of the thiol compound derivatives represented by the formula(9) (sometimes referred to as “derivative c” hereinafter) wherein X¹ andX² are the same and X¹ is represented by the following formula (2)include thiol compound derivatives shown in the following Table 3(Tables 3-1 to 3-4). (9)

(2) Thiol compound derivative Derivative A R³ R¹ R² Tables 3-1 c1 c Na OH H methyl group c2 c Na O H H ethyl group c3 c Na O H H n-propyl groupc4 c Na O H H isopropyl group c5 c Na O H H n-butyl group c6 c Na O H Hisobutyl group c7 c Na O H H sec-butyl group c8 c Na O H H tert-butylgroup c9 c Na O H H pentyl group c10 c Na O H H hexyl group c11 c Na O HH heptyl group c12 c Na O H H octyl group c13 c Na O H H 2-ethylhexylgroup c14 c Na O H H decyl group c15 c Na O H H cetyl group c16 c Na O HH stearyl group c17 c Na O H H 1-menthyl group c18 c Na O H Hpropanedienyl group c19 c Na O H H isopropenyl group c20 c Na O H H3-butynyl group c21 c Na O H H 3-methyl-2-butenyl group c22 c Na O H Hallyl group c23 c Na O H H 2-methylallyl group c24 c Na O H H propargylgroup c25 c Na O H H 3-phenylpropargyl group c26 c Na O H H residuewherein one hydroxyl group of ethylene glycol is removed c27 c Na O H Hresidue wherein one hydroxyl group of propylene glycol is removed c28 cNa O H H residue wherein one hydroxyl group of butylene glycol isremoved c29 c Na O H H residue wherein one hydroxyl group of diethyleneglycol is removed c30 c Na O H H residue wherein one hydroxyl group ofdipropylene glycol is removed c31 c Na O H H residue wherein onehydroxyl group of dibutylene glycol is removed c32 c Na O H H residuewherein one hydroxyl group of diethylene glycol monobutyl ether isremoved Tables 3-2 c33 c Na O H H residue wherein one hydroxyl group oftriethylene glycol is removed c34 c Na O H H residue wherein onehydroxyl group of tripropylene glycol is removed c35 c Na O H H residuewherein one hydroxyl group of tributylene glycol is removed c36 c Na O HH residue wherein one hydroxyl group of tetraethylene glycol is removedc37 c Na O H H residue wherein one hydroxyl group of tetrapropyleneglycol is removed c38 c Na O H H residue wherein one hydroxyl group oftetrabutylene glycol is removed c39 c Na O H H residue wherein ahydroxyl group of acetone oxime group is removed c40 c Na O H H residuewherein one hydroxyl group of triethanolamine is removed c41 c Na O H Hresidue wherein one hydroxyl group of diethanolamine is removed c42 c NaO H H residue wherein a hydroxyl group of dimethylaminoethanol isremoved c43 c Na O H H residue wherein a hydroxyl group oftrimethylsilyl alcohol is removed c44 c Na O H H residue wherein ahydroxyl group of triethylsilyl alcohol is removed c45 c Na O H Hresidue wherein a hydroxyl group of cyclohexyl alcohol is removed c46 cNa O H H residue wherein a hydroxyl group of menthol is removed c47 c NaO H H residue wherein a hydroxyl group of naphthyl alcohol is removedc48 c Na O H H 1-chloroethyl group c49 c Na O H H 2-chloroethyl groupc50 c Na O H H 1-bromoethyl group c51 c Na O H H 2-bromoethyl group c52c Na O H H methoxyethyl group c53 c Na O H H 2-butoxyethyl group c54 cNa O H H methoxyethoxyethyl group c55 c Na O H H dimethylaminoethylgroup c56 c Na O H H 2-(diethylamino)ethyl group c56 c Na O H H3-dimethylaminopropyl group c57 c Na O H H aminoethyl group c58 c Na O HH trimethylsilylethyl group c59 c Na O H H trimethylsiloxyethyl groupTables 3-3 c60 c Na O H H 2-acetoxyethyl group c61 c Na O H H2-piperidinoethyl group c62 c Na O H H phenyl group c63 c Na O H Hmethoxyphenyl group c64 c Na O H H o-tolyl group c65 c Na O H Ho-isopropylphenyl group c66 c Na O H H p-nitrophenyl group c67 c Na O HH 2-nitrophenyl group c68 c Na O H H 3-nitrophenyl group c69 c Na O H Hp-fluorophenyl group c70 c Na O H H p-methoxyphenyl group c71 c Na O H Hp-aminophenyl group c72 c Na O H H N-methylaminophenyl group c73 c Na OH H p-(dimethylamino)phenyl group c74 c Na O H H 4-acetylphenyl groupc75 c Na O H H p-iodophenyl group c76 c Na O H H p-chlorophenyl groupc77 c Th O H H p-bromophenyl group c78 c Na O H H 2,4,6-trichlorophenylgroup o79 c Na O H H 2,4,6-tribromophenyl group c80 c Na O H H2,4,6-trimethylphenyl group c81 c Na O H H 2,4-dichlorophenyl group c82c Na O H H 2,4-dibromophenyl group c83 c Na O H H 2,4-dimethylphenylgroup c84 c Na O H H —CH₂OCH═CH₂ c85 c Na O H H —CH₂CH₂OCH═CH₂ c86 c NaO H H —CH₂CH₂CH₂OCH═CH₂ c87 c Na O H H —CH₂CH₂CH₂CH₂OCH═CH₂ c88 c Na O HH —CH₂CH₂OCH₂CH₂OCH═CH₂ c89 c Na O H H —CH₂CH₂OCH₂CH₂OCH₂CH₂OCH═CH₂ c90c Na O H H —CH₂CH₂N(CH₂CH₂OH)CH₂CH₂OCH═CH₂ c91 c Na O H H —Ph—OCH═CH₂c92 c Na O H H —Ph—N═N—Ph—OCH═CH₂ c93 c Na O H H —Ph—C(CH₃)₂—Ph—OCH═CH₂c94 c Na O H H -cyclohexylene-OCH═CH₂ c95 c Na O H H 1-phenylethyl groupc96 c Na O H H benzyl group Tables 3-4 c97 c Na

c98 c Na

c99 c Na

c100 c Na

c101 c Na

c102 c Na S H H 3-(trimethylsilyl)propyl group c103 c Na S H H2-hydroxyethyl group c104 c Na S H H 2-(N-morpholino)ethyl group c105 cNa S H H 2-(N-β-hydroxyethyl)aminoethyl group c106 c Na S H H2-aminoethyl group c107 c Na S H H p-chlorophenyl group c108 c Na S H Hphenyl group c109 c Na S H H vinyl group c110 c Na O Me H methyl groupc111 c Na O Me H ethyl group c112 c Na O Et H methyl group c113 c Na OEt H ethyl group c114 C Na O Ph— H methyl group c115 c Na O Ph— H ethylgroup

Dithiol Compound Derivative

The thiol compound derivative according to the present invention is, forexample, a dithiol compound derivative represented by the followingformula (10) (sometimes referred to as “derivative d” hereinafter),which is a derivative of a dithiol compound.

In the formula (10), X¹ and X² are each a group represented by thefollowing formula (2).

In the formula (10), X¹ and X² are each the same as X¹ in the formula(1), and X¹ and X² may be the same or different, preferably the same.The formula (2) is the same as that previously described.

In the formula (10), R⁵ is a group selected from the following groups(g) to (k).

(g) A group selected from a hydrogen atom, an alkyl group, an alkenylgroup, an alkynyl group, a phenyl group, an aralkyl group and —NH₂.

Of these, a hydrogen atom, an alkyl group and a phenyl group arepreferable.

The alkyl group is preferably an alkyl group of 1 to 25 carbon atoms,more preferably an alkyl group of 1 to 18 carbon atoms. The alkyl groupmay be any of straight-chain, branched and cyclic alkyl groups. Examplesof such alkyl groups include methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl,2-ethylhexyl, decyl, cetyl, stearyl and 1-menthyl. Of these, methyl andethyl are preferable.

The alkenyl group is preferably an alkenyl group of 1 to 20 carbonatoms, more preferably an alkenyl group of 1 to 10 carbon atoms.Examples of such alkenyl groups include propanedienyl, isopropenyl,3-methyl-2-butenyl, allyl and 2-methylallyl. Of these, isopropenyl ispreferable.

The alkynyl group is preferably an alkynyl group of 1 to 20 carbonatoms, more preferably an alkynyl group of 1 to 10 carbon atoms.Examples of such alkynyl groups include propargyl and 1-phenylpropargyl.Of these, propargyl is preferable.

The aralkyl group is preferably an aralkyl group of 1 to 20 carbonatoms, more preferably an aralkyl group of 1 to 10 carbon atoms. Anexample of such an aralkyl group is 4-phenylbutyl.

Examples of the phenyl groups include phenyl (C₆H₅—), methoxyphenyl,o-tolyl, p-nitrophenyl, 2-nitrophenyl, 3-nitrophenyl, p-fluorophenyl,p-methoxyphenyl, p-aminophenyl, N-methylaminophenyl,p-(dimethylamino)phenyl, 4-acetylphenyl, p-iodophenyl, p-chlorophenyl,2-piperidinoethyl, 2,4,6-trichlorophenyl, 2,4,6-trimethylphenyl,2,4,6-tribromophenyl, 2,4-dichlorophenyl, 2,4-dibromophenyl and2,4-dimethylphenyl. Of these, phenyl is preferable.

(h) A dialkylamino group represented by the following formula (11):—NR⁶R⁷  (11)wherein R⁶ and R⁷ are each a group selected from an alkyl group, analkenyl group, an alkynyl group, an aralkyl group, a benzyl group, anallyl group, a cycloalkyl group, a fluoroalkyl group and a phenyl group,and R⁶ and R⁷ may be the same or different. Of these, an alkyl group andan alkenyl group are preferable.

The alkyl group is preferably an alkyl group of 1 to 25 carbon atoms,more preferably an alkyl group of 1 to 18 carbon atoms. The alkyl groupmay be any of straight-chain, branched and cyclic alkyl groups. Examplesof such alkyl groups include methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl,2-ethylhexyl, decyl, cetyl, stearyl and 1-menthyl. Of these, methyl andethyl are preferable.

The alkenyl group is preferably an alkenyl group of 1 to 20 carbonatoms, more preferably an alkenyl group of 1 to 10 carbon atoms.Examples of such alkenyl groups include propanedienyl, isopropenyl,3-methyl-2-butenyl, allyl and 2-methylallyl. Of these, isopropenyl ispreferable.

The alkynyl group is preferably an alkynyl group of 1 to 20 carbonatoms, more preferably an alkynyl group of 1 to 10 carbon atoms.Examples of such alkynyl groups include propargyl and 1-phenylpropargyl.Of these, propargyl is preferable.

The aralkyl group is preferably an aralkyl group of 1 to 20 carbonatoms, more preferably an aralkyl group of 1 to 10 carbon atoms. Anexample of such an aralkyl group is methylbenzyl.

Examples of the benzyl groups include benzyl and 1-phenylethyl.

Examples of the cycloalkyl groups include cyclohexyl and cyclopentyl.

Examples of the fluoroalkyl groups include tetrafluoroethyl.

(i) A monoalkylamino group represented by the following formula (12)—NHR⁸  (12)wherein R⁸ is a group selected from an alkyl group, an alkenyl group, analkynyl group, an aralkyl group, a benzyl group, an allyl group, acycloalkyl group, a fluoroalkyl group, an anilino group, ahydroxyanilino group and a phenyl group. Of these, an alkyl group ispreferable.

Examples of the alkyl groups, the alkenyl groups, the alkynyl groups,the aralkyl groups, the benzyl groups, the allyl groups, the cycloalkylgroups and the fluoroalkyl groups include the same groups as previouslydescribed with respect to R⁶ and R⁷.

Examples of the anilino groups include anilino and p-methylanilino.

Examples of the hydroxyanilino groups include groups derived from o-, m-and p-hydroxyaniline derivatives.

(j) A group represented by the following formula (13):—OR⁹  (13)wherein R⁹ is a group selected from an alkyl group, a phenyl group, analkenyl group, an aralkyl group, a halogenophenyl group, a naphthylgroup and a cycloalkyl group. Of these, preferable are an alkyl groupand a phenyl group.

The alkyl group is preferably an alkyl group of 1 to 25 carbon atoms,more preferably an alkyl group of 1 to 18 carbon atoms. The alkyl groupmay be any of straight-chain, branched and cyclic alkyl groups. Examplesof such alkyl groups include methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl,2-ethylhexyl, decyl, cetyl, stearyl and 1-menthyl. Of these, methyl andethyl are preferable.

The alkenyl group is preferably an alkenyl group of 1 to 20 carbonatoms, more preferably an alkenyl group of 1 to 10 carbon atoms.Examples of such alkenyl groups include propanedienyl, isopropenyl,3-methyl-2-butenyl, allyl and 2-methylallyl. Of these, isopropenyl ispreferable.

The aralkyl group is preferably an aralkyl group of 1 to 20 carbonatoms, more preferably an aralkyl group of 1 to 10 carbon atoms. Anexample of such an aralkyl group is 4-phenylbutyl.

Examples of the halogenophenyl groups include p-iodophenyl,p-chlorophenyl, p-bromophenyl, 2,4-dichlorophenyl, 2,4-dibromophenyl,2,4-diiodophenyl, 2,4,6-trichlorophenyl and 2,4,6-tribromophenyl. Ofthese, p-chlorophenyl is preferable.

Examples of the cycloalkyl groups include cyclohexyl and cyclopentyl.

(k) A group represented by the following formula (14):—SR¹⁰  (14)wherein R¹⁰ is a group selected from an alkyl group, an alkenyl group,an alkynyl group, a phenyl group, an aralkyl group, a halogenophenylgroup, a naphthyl group and a cycloalkyl group. Of these, an alkyl groupis preferable.

Examples of the alkyl groups, the alkenyl groups, the aralkyl groups,the halogenphenyl groups, the naphthyl groups and the cycloalkyl groupsinclude those of the alkyl groups, the alkenyl groups, the aralkylgroups, the halogenphenyl groups, the naphthyl groups and the cycloalkylgroups previously described with respect to R⁹.

The alkynyl group is preferably an alkynyl group of 1 to 20 carbonatoms, more preferably an alkynyl group of 1 to 10 carbon atoms.Examples of such alkynyl groups include propargyl and 1-phenylpropargyl.Of these, propargyl is preferable.

Examples of the phenyl groups include phenyl (C₆H₅—), methoxyphenyl,o-tolyl, p-nitrophenyl, 2-nitrophenyl, 3-nitrophenyl, p-fluorophenyl,p-methoxyphenyl, p-aminophenyl, N-methylaminophenyl,p-(dimethylamino)phenyl, 4-acetylphenyl, p-iodophenyl, p-chlorophenyl,2-piperidinoethyl, 2,4,6-trichlorophenyl, 2,4,6-trimethylphenyl,2,4,6-tribromophenyl, 2,4-dichlorophenyl, 2,4-dibromophenyl and2,4-dimethylphenyl. Of these, phenyl and methoxyphenyl are preferable.

In the thiol compound derivative of the invention, R¹ and R² in theformula (11) may form a ring. When R¹ and R² form a ring, R¹ and R² areeach preferably an alkyl group, and the alkyl group may have asubstituent.

In the above case, R³ is preferably a hydrogen atom, and the ring formedfrom R¹ and R² is preferably represented by the following formula (7):

wherein n is 3 or 4.

The constituent of the above-mentioned cyclic structure may have asubstituent.

Another dithiol compound derivative that is the thiol compoundderivative according to the present invention is a thiol compoundderivative represented by the following formula (15) (sometimes referredto as “derivative e” hereinafter):

wherein X¹ is a group represented by the following formula (2):

In the formula (15), R⁵ is the same as R⁵ in the formula (10). Theformula (2) is the same as that previously described.

Another dithiol compound derivative that is the thiol compoundderivative according to the present invention is a thiol compoundderivative represented by the following formula (16) (sometimes referredto as “derivative f” hereinafter):

wherein X¹ is a group represented by the following formula (2):

In the formula (16), M is an alkali metal or an alkaline earth metal.Examples of the alkali metals include sodium and potassium. Examples ofthe alkaline earth metals include calcium, magnesium and barium. Ofthese, sodium is preferable.

R⁵ is the same as R⁵ in the formula (10). The formula (2) is the same asthat previously described.

Described below are examples of “preferred substituents R⁵” in the thiolcompound derivative represented by the formula (10):

wherein X¹ and X² are each a group represented by the following formula(2):

That is to say, there can be mentioned a hydrogen atom, a methyl group,a phenyl group, an amino group, a dihexylamino group, abis(2-hexyl)amino group, a diethylamino group, a dicyclohexylaminogroup, a diphenylamino group, a dibenzylamino group, a diallylaminogroup, a didodecylamino group, a dibutylamino group, a dimethylaminogroup, a phenylamino group, a 3,5-di-tert-butyl-4-hydroxyanilino group,a stearylamino group, an ethylamino group, a hexylamino group, acis-9-octadecenylamino group, a cyclohexylamino group, a4-anilino-N-isopropylanilino group, a methoxy group, a 1-naphthyloxygroup, a m-chlorophenoxy group, a 2,4-dimethylphenoxy group and aphenoxy group. Examples of “more preferred substituents R⁵” include ahydrogen atom, a methyl group, a phenyl group, a dibutylamino group, amethoxy group and a phenoxy group.

Examples of preferred substituents R⁵ and more preferred substituents R⁵in the derivative e represented by the formula (15) and the derivative frepresented by the formula (16) are the same as those described abovewith respect to the thiol compound derivative d represented by theformula (10).

Particularly preferable is a thiol compound derivative wherein R⁵ is anyone of (g) to (k) and in the formula (2) A is an oxygen atom, R¹ is ahydrogen atom, R² is an alkyl group or a residue wherein a hydroxylgroup is removed from (poly)alkylene glycol, and R³ is a hydrogen atom.

Examples of the thiol compound derivatives d, e and f represented by theformulas (10), (15) and (16), respectively, include thiol compoundderivatives d, e and f having, as A, R¹, R² and R³ of X¹, substituentsshown in the following Table 4 (Tables 4-1 to 4-4), Table 5 (Table 5-1to 5-4) and Table 6 (Table 6-1 to 6-4). Thiol compound derivativeDerivative A R³ R¹ R² Tables 4-1 d1 d O H H methyl group d2 d O H Hethyl group d3 d O H H n-propyl group d4 d O H H isopropyl group d5 d OH H n-butyl group d6 d O H H isobutyl group d7 d O H H sec-butyl groupd8 d O H H tert-butyl group d9 d O H H pentyl group dlO d O H H hexylgroup dli d O H H heptyl group d12 d O H H octyl group d13 d O H H2-ethylhexyl group d14 d O H H decyl group d15 d O H H cetyl group d16 dO H H stearyl group d17 d O H H 1-menthyl group d18 d O H Hpropanedienyl group d19 d O H H isopropenyl group d20 d O H H 3-butynylgroup d21 d O H H 3-methyl-2-butenyl group d22 d O H H allyl group d23 dO H H 2-methylallyl group d24 d O H H propargyl group d25 d O H H3-phenylpropargyl group d26 d O H H residue wherein one hydroxyl groupof ethylene glycol is removed d27 d O H H residue wherein one hydroxylgroup of propylene glycol is removed d28 d O H H residue wherein onehydroxyl group of butylene glycol is removed d29 d O H H residue whereinone hydroxyl group of diethylene glycol is removed d30 d O H H residuewherein one hydroxyl group of dipropylene glycol is removed d31 d O H Hresidue wherein one hydroxyl group of dibutylene glycol is removed d32 dO H H residue wherein one hydroxyl group of diethylene glycol monobutylether is removed d33 d O H H residue wherein one hydroxyl group oftriethylene glycol is removed d34 d O H H residue wherein one hydroxylgroup of tripropylene glycol is removed d35 d O H H residue wherein onehydroxyl group of tributylene glycol is removed Table 4-2 d36 d O H Hresidue wherein one hydroxyl group of tetraethylene glycol is removedd37 d O H H residue wherein one hydroxyl group of tetrapropylene glycolis removed d38 d O H H residue wherein one hydroxyl group oftetrabutylene glycol is removed d39 d O H H residue wherein a hydroxylgroup of oxime group is removed d40 d O H H residue wherein one hydroxylgroup of triethanolamine is removed d41 d O H H residue wherein onehydroxyl group of diethanolamine is removed d42 d O H H residue whereina hydroxyl group of dimethylaminoethanol is removed d43 d O H H residuewherein a hydroxyl group of trimethylsilyl alcohol is removed d44 d O HH residue wherein a hydroxyl group of triethylsilyl alcohol is removedd45 d O H H residue wherein a hydroxyl group of cyclohexyl alcohol isremoved d46 d O H H residue wherein a hydroxyl group of is removed d47 dO H H residue wherein a hydroxyl group of naphthyl alcohol is removedd48 d O H H 1-chloroethyl group d49 d O H H 2-chloroethyl group d50 d OH H 1-bromoethyl group d51 d O H H 2-bromoethyl group d52 d O H Hethoxyethyl group d53 d O H H 2-butoxyethyl group d54 d O H Hmethoxyethoxyethyl group d55 d O H H dimethylaminoethyl group d56 d O HH 2-(diethylamino)ethyl group d56 d O H H 3-dimethylaminopropyl groupd57 d O H H aminoethyl group d58 d O H H trimethylsilylethyl group d59 dO H H trimethylsiloxyethyl group d60 d O H H 2-acetoxyethyl group d61 dO H H 2-piperidinoethyl group d62 d O H H phenyl group d63 d O H Hmethoxyphenyl group d64 d O H H o-tolyl group d65 d O H Ho-isopropylphenyl group d66 d O H H p-nitrophenyl group d67 d O H H2-nitrophenyl group d68 d O H H 3-nitrophenyl group d69 d O H Hp-fluorophenyl group d70 d O H H p-methoxyphenyl group Tables 4-3 d71 dO H H p-aminophenyl group d72 d O H H N-methylaminophenyl group d73 d OH H p-(dimethylamino)phenyl group d74 d O H H 4-acetylphenyl group d75 dO H H p-iodophenyl group d76 d O H H p-chlorophenyl group d77 d O H Hp-bromophenyl group d78 d O H H 2,4,6-trichlorophenyl group d79 d O H H2,4,6-tribromophenyl group dBO d O H H 2,4,6-trimethylphenyl group d81 dO H H 2,4-dichlorophenyl group d82 d O H H 2,4-dibromophenyl group d83 dO H H 2,4-dimethylphenyl group d84 d O H H —CH₂OCH═CH₂ d85 d O H H—CH₂CH₂OCH═CH₂ d86 d O H H —CH₂CH₂CH₂OCH═CH₂ d87 d O H H—CH₂CH₂CH₂CH₂OCH═CH₂ d88 d O H H —CH₂CH₂OCH₂CH₂OCH═CH₂ d89 d O H H—CH₂CH₂OCH₂CH₂OCH₂CH₂OCH═CH₂ d90 d O H H —CH₂CH₂N(CH₂CH₂OH)CH₂CH₂OCH═CH₂d91 d O H H —Ph—OCH═CH₂ d92 d O H H —Ph—N═N—Ph—OCH═CH₂ d93 d O H H—Ph—C(CH₃)₂—Ph—OCH═CH₂ d94 d O H H -cyclohexylene-OCH═CH₂ d95 d O H H1-phenylethyl group d96 d O H H benzyl group d97 d

d98 d

Tables 4-4 d99 d

d100 d

d101 d

d102 d S H H 3-(trimethylsilyl)propyl group d103 d S H H 2-hydroxyethylgroup d104 d S H H 2-(N-morpholino)ethyl group d105 d S H H2-(N-β-hydroxyethyl)aminoethyl group d106 d S H H 2-aminoethyl groupd107 d S H H p-chlorophenyl group d108 d S H H phenyl group d109 d S H Hvinyl group d110 d O Me H methyl group d111 d O Me H ethyl group d112 dO Et H methyl group d113 d O Et H ethyl group d114 d O Ph— H methylgroup d115 d O Ph— H ethyl group

Thiol compound derivative Derivative A R³ R¹ R² Tables 5-1 e1 e O H Hmethyl group e2 e O H H ethyl group e3 e O H H n-propyl group e4 e O H Hisopropyl group e5 e O H H n-butyl group e6 e O H H isobutyl group e7 eO H H sec-butyl group e8 e O H H tert-butyl group e9 e O H H pentylgroup e10 e O H H hexyl group e11 e O H H heptyl group e12 e O H H octylgroup e13 e O H H 2-ethylhexyl group e14 e O H H decyl group e15 e O H Hcetyl group e16 e O H H stearyl group e17 e O H H 1-menthyl group e18 eO H H propanedienyl group e19 e O H H isopropenyl group e20 e O H H3-butynyl group e21 e O H H 3-methyl-2-butenyl group e22 e O H H allylgroup e23 e O H H 2-methylallyl group e24 e O H H propargyl group e25 eO H H 3-phenylpropargyl group e26 e O H H residue wherein one hydroxylgroup of ethylene glycol is removed e27 e O H H residue wherein onehydroxyl group of propylene glycol is removed e28 e O H H residuewherein one hydroxyl group of butylene glycol is removed e29 e O H Hresidue wherein one hydroxyl group of diethylene glycol is removed e30 eO H H residue wherein one hydroxyl group of dipropylene glycol isremoved e31 e O H H residue wherein one hydroxyl group of dibutyleneglycol is removed e32 e O H H residue wherein one hydroxyl group ofdiethylene glycol monobutyl ether is removed e33 e O H H residue whereinone hydroxyl group of triethylene glycol is removed e34 e O H H residuewherein one hydroxyl group of tripropylene glycol is removed e35 e O H Hresidue wherein one hydroxyl group of tributylene glycol is removedTables 5-2 e36 e O H H residue wherein one hydroxyl group oftetraethylene glycol is removed e37 e O H H residue wherein one hydroxylgroup of tetrapropylene glycol is removed e38 e O H H residue whereinone hydroxyl group of tetrabutylene glycol is removed e39 e O H Hresidue wherein a hydroxyl group of acetone oxime group is removed e40 eO H H residue wherein one hydroxyl group of triethanolamine is removede41 e O H H residue wherein one hydroxyl group of diethanolamine isremoved e42 e O H H residue wherein a hydroxyl group ofdimethylaminoethanol is removed e43 e O H H residue wherein a hydroxylgroup of trimethylsilyl alcohol is removed e44 e O H H residue wherein ahydroxyl group of triethylsilyl alcohol is removed e45 e O H H residuewherein a hydroxyl group of cyclohexyl alcohol is removed e46 e O H Hresidue wherein a hydroxyl group of menthol is removed e47 e O H Hresidue wherein a hydroxyl group of naphthyl alcohol is removed e48 e OH H 1-chloroethyl group e49 e O H H 2-chloroethyl group e50 e O H H1-bromoethyl group e51 e O H H 2-bromoethyl group e52 e O H Hmethoxyethyl group e53 e O H H 2-butoxyethyl group e54 e O H Hmethoxyethoxyethyl group e55 e O H H dimethylaminoethyl group e56 e O HH 2-(diethylamino)ethyl group e56 e O H H 3-dimethylaminopropyl groupe57 e O H H aminoethyl group e58 e O H H trimethylsilylethyl group e59 eO H H trimethylsiloxyethyl group e60 e O H H 2-acetoxyethyl group e61 eO H H 2-piperidinoethyl group e62 e O H H phenyl group e63 e O H Hmethoxyphenyl group e64 e O H H o-tolyl group e65 e O H Ho-isopropylphenyl group e66 e O H H p-nitrophenyl group e67 e O H H2-nitrophenyl group e68 e O H H 3-nitrophenyl group e69 e O H Hp-fluorophenyl group e70 e O H H p-methoxyphenyl group e71 e O H Hp-aminophenyl group e72 e O H H N-methylaminophenyl group Tables 5-3 e73e O H H p-(dimethylamino)phenyl group e74 e O H H 4-acetylphenyl groupe75 e O H H p-iodophenyl group e76 e O H H p-chlorophenyl group e77 e OH H p-bromophenyl group e78 e O H H 2,4,6-trichlorophenyl group e79 e OH H 2,4,6-tribromophenyl group e80 e O H H 2,4,6-trimethylphenyl groupe81 e O H H 2,4-dichlorophenyl group e82 e O H H 2,4-dibromophenyl groupe83 e O H H 2,4-dimethylphenyl group e84 e O H H —CH₂OCH═CH₂ e85 e O H H—CH₂CH₂OCH═CH₂ e86 e O H H —CH₂CH₂CH₂OCH═CH₂ e87 e O H H—CH₂CH₂CH₂CH₂OCH═CH₂ e88 e O H H —CH₂CH₂OCH₂CH₂OCH═CH₂ e89 e O H H—CH₂CH₂OCH₂CH₂OCH₂CH₂OCH═CH₂ e90 e O H H —CH₂CH₂N(CH₂CH₂OH)CH₂CH₂OCH═CH₂e91 e O p H —Ph—OCH═CH₂ e92 e O H H —Ph—N═N—Ph—OCH═CH₂ e93 e O H H—Ph—C(CH₃)₂—Ph—OCH═CH₂ e94 e O H H -cyclohexylene-OCH═CH₂ e95 e O H H1-phenylethyl group e96 e O H H benzyl group e97 e

e98 e

e99 e

Tables 5-4 e100 e

e101 e

e102 e S H H 3-(trimethylsilyl)propyl group e103 e S H H 2-hydroxyethylgroup e104 e S H H 2-(N-morpholino)ethyl group e105 e S H H2-(N-β-hydroxyethyl)aminoethyl group e106 e S H H 2-aminoethyl groupe107 e S H H p-chlorophenyl group e108 e S H H phenyl group e109 e S H Hvinyl group e110 e O Me H methyl group e111 e O Me H ethyl group e112 eO Et H methyl group e113 a O Et H ethyl group e114 e O Ph— H methylgroup e115 a O Ph— H ethyl group

Thiol compound derivative Derivative M A R³ R¹ R² Tables 6-1 f1 f Na O HH methyl group f2 f Na O H H ethyl group f3 f Na O H H n-propyl group f4f Na O H H isopropyl group f5 f Na O H H n-butyl group f6 f Na O H Hisobutyl group f7 f Na O H H sec-butyl group f8 f Na O H H tert-butylgroup f9 f Na O H H pentyl group f10 f Na O H H hexyl group f11 f Na O HH heptyl group f12 f Na O H H octyl group f13 f Na O H H 2-ethylhexylgroup f14 f Na O H H decyl group f15 f Na O H H cetyl group f16 f Na O HH stearyl group f17 f Na O H H 1-menthyl group f18 f Na O H Hpropanedienyl group f19 f Na O H H isopropenyl group f20 f Na O H H3-butynyl group f21 f Na O H H 3-methyl-2-butenyl group f22 f Na O H Hallyl group f23 f Na O H H 2-methylallyl group f24 f Na O H H propargylgroup f25 f Na O H H 3-phenylpropargyl group f26 f Na O H H residuewherein one hydroxyl group of ethylene glycol is removed f27 f Na O H Hresidue wherein one hydroxyl group of propylene glycol is removed f28 fNa O H H residue wherein one hydroxyl group of butylene glycol isremoved f29 f Na O H H residue wherein one hydroxyl group of diethyleneglycol is removed f30 f Na O H H residue wherein one hydroxyl group ofdipropylene glycol is removed f31 f Na O H H residue wherein onehydroxyl group of dibutylene glycol is removed f32 f Na O H H residuewherein one hydroxyl group of diethylene glycol monobutyl ether isremoved Tables 6-2 f33 f Na O H H residue wherein one hydroxyl group oftriethylene glycol is removed f34 f Na O H H residue wherein onehydroxyl group of tripropylene glycol is removed f35 f Na O H H residuewherein one hydroxyl group of tributylene glycol is removed f36 f Na O HH residue wherein one hydroxyl group of tetraethylene glycol is removedf37 f Na O H H residue wherein one hydroxyl group of tetrapropyleneglycol is removed f38 f Na O H H residue wherein one hydroxyl group oftetrabutylene glycol is removed f39 f Na O H H residue wherein ahydroxyl group of acetone oxime group is removed f40 f Na O H H residuewherein one hydroxyl group of triethanolamine is removed f41 f Na O H Hresidue wherein one hydroxyl group of diethanolamine is removed f42 f NaO H H residue wherein a hydroxyl group of dimethylaminoethanol isremoved f43 f Na O H H residue wherein a hydroxyl group oftrimethylsilyl alcohol is removed f44 f Na O H H residue wherein ahydroxyl group of triethylsilyl alcohol is removed f45 f Na O H Hresidue wherein a hydroxyl group of cyclohexyl alcohol is removed f46 fNa O H H residue wherein a hydroxyl group of menthol is removed f47 f NaO H H residue wherein a hydroxyl group of naphthyl alcohol is removedf48 f Na O H H 1-chloroethyl group f49 f Na O H H 2-chloroethyl groupf50 f Na O H H 1-bromoethyl group f51 f Na O H H 2-bromoethyl group f52f Na O H H methoxyethyl group f53 f Na O H H 2-butoxyethyl group f54 fNa O H H methoxyethoxyethyl group f55 f Na O H H dimethylaminoethylgroup f56 f Na O H H 2-(diethylamino)ethyl group f56 f Na O H H3-dimethylaminopropyl group f57 f Na O H H aminoethyl group f58 f Na O HH trimethylsilylethyl group f59 f Na O H H trimethylsiloxyethyl groupTables 6-3 f60 f Na O H H 2-acetoxyethyl group f61 f Na O H H2-piperidinoethyl group f62 f Na O H H phenyl group f63 f Na O H Hmethoxyphenyl group f64 f Na O H H o-tolyl group f65 f Na O H Ho-isopropylphenyl group f66 f Na O H H p-nitrophenyl group f67 f Na O HH 2-nitrophenyl group f68 f Na O H H 3-nitrophenyl group f69 f Na O H Hp-fluorophenyl group f70 f Na O H H p-methoxyphenyl group f71 f Na O H Hp-aminophenyl group f72 f Na O H H N-methylaminophenyl group f73 f Na OH H p-(dimethylamino)phenyl group f74 f Na O H H 4-acetylphenyl groupf75 f Na O H H p-iodophenyl group f76 f Na O H H p-chlorophenyl groupf77 f Na O H H p-bromophenyl group f78 f Na O H H 2,4,6-trichlorophenylgroup f79 f Na O H H 2,4,6-tribromophenyl group f80 f Na O H H2,4,6-trimethylphenyl group f81 f Na O H H 2,4-dichlorophenyl group f82f Na O H H 2,4-dibromophenyl group f83 f Na O H H 2,4-dimethylphenylgroup f84 f Na O H H —CH₂OCH═CH₂ f85 f Na O H H —CH₂CH₂OCH═CH₂ f86 f NaO H H —CH₂CH₂CH₂OCH═CH₂ f87 f Na O H H —CH₂CH₂CH₂CH₂OCH═CH₂ f88 f Na O HH —CH₂CH₂OCH₂CH₂OCH═CH₂ f89 f Na O H H —CH₂CH₂OCH₂CH₂OCH₂CH₂OCH═CH₂ f90f Na O H H —CH₂CH₂N(CH₂CH₂OH)CH₂CH₂OCH═CH₂ f91 f Na O H H —Ph—OCH═CH₂f92 f Na O H H —Ph—N═N—Ph—OCH═CH₂ f93 f Na O H H —Ph—C(CH₃)₂—Ph—OCH═CH₂f94 f Na O H H -cyclohexylene-OCH═CH₂ f95 f Na O H H 1-phenylethyl groupf96 f Na O H H benzyl group Tables 6-4 f97 f Na

f98 f Na

f99 f Na

f100 f Na

f101 f Na

f102 f Na S H H 3-(trimethylsilyl)propyl group f103 f Na S H H2-hydroxyethyl group f104 f Na S H H 2-(N-morpholino)ethyl group f105 fNa S H H 2-(N-β-hydroxyethyl)aminoethyl group f106 f Na S H H2-aminoethyl group f107 f Na S H H p-chlorophenyl group f108 f Na S H Hphenyl group f109 f Na S H H vinyl group f110 f Na O Me H methyl groupf111 f Na O Me H ethyl group f112 f Na O Et H methyl group f113 f Na OEt H ethyl group f114 f Na O Ph— H methyl group f115 f Na O Ph— H ethylgroup

As the thiol compound derivative of the invention, a monothiol compoundderivative wherein one of the substituents —SX¹ and —SX² of the dithiolcompound derivative represented by the formula (10) is furthersubstituted with —R⁵ is also available in addition to the trithiolcompound derivative and the dithiol compound derivative. In themonothiol compound derivative, R⁵ and X¹ (or X²) are the same of R⁵ andX¹ of the dithiol compound derivative represented by the formula (10).

Process for Preparing Thiol Compound Derivative

The thiol compound derivative of the invention is obtained by bonding apart or all of thiol groups (—SH) of a thiol compound having 1 to 3thiol groups in one molecule to a double bond part of a vinyl ether orthe like. In other words, the thiol compound derivative can be obtainedby replacing a hydrogen atom of a thiol group of a thiol compound with asubstituent derived from a vinyl ether or the like.

There is no specific limitation on the process for preparing the thiolcompound derivative, and publicly known processes capable of forming adesired substituent are employable.

For example, a thiol compound, such as triazinethiol or triazinedithiol,and monovinyl ether, aldehyde, ketone or the like are contacted in givenamounts, whereby the thiol compound derivative wherein given amounts ofthiol groups (—SH group) are substituted can be obtained.

The thiol compound derivative can also be obtained from a thiol compoundand a polyvalent vinyl ether compound. In this case, a crosslinkedproduct of the thiol compound is sometimes formed by virtue of thepolyvalent vinyl ether.

In the contact of the thiol compound with the vinyl ether or the like,an acid catalyst can be used when needed.

Examples of the thiol compound derivatives thus obtained includederivatives wherein the thiol group and the vinyl group of the vinylethers are reacted in the same amounts and all of hydrogen atoms of thethiol groups are replaced with substituents derived from the vinylethers, derivatives wherein one thiol group remains, and derivativeswherein a salt is formed from the remaining thiol group with the aid ofan alkali metal, a polyvalent metal or an onium base such as quaternaryammonium base, phosphonium base or pyridinium base.

Next, the thiol compound, the vinyl ethers, etc. are described. Inaddition, the catalyst that is optionally used for the reaction of thethiol compound with the vinyl ether or the like and the process forpreparing the thiol compound derivative are also described in detail.

Thiol Compound

The thiol compound for use in the invention is preferably a compoundwherein two or more thiol groups per molecule are bonded, and any ofsuch thiol compounds is employable.

Examples of the thiol compounds include phenylthiol such asdimercaptobenzene, thiocarboxylic acids, thiol compounds such asthiadiazole, mercaptoalkyltrialkoxysilanes such asγ-mercaptopropyltrimethoxysilane, aliphatic dithiols such as1,10-dimercaptodecane, 1,3,5-triazine-2,4,6-trithiol represented by thefollowing formula (18), and triazinethiols represented by the followingformula (19).

In addition to the trithiol compounds and the dithiol compounds,monothiol compounds wherein one of the thiol groups (—SH) in the aboveformula (19) is further substituted with R⁵ are also employable.

R⁵ in the formula (19) is the same as R⁵ in the aforesaid formula (10).

Preferred examples of the dithiol compounds represented by the formula(19) include:

-   s-triazine-2,4-dithiol,-   6-methyl-s-triazine-2,4-dithiol,-   6-phenyl-s-triazine-2,4-dithiol,-   6-amino-s-triazine-2,4-dithiol,-   6-dihexylamino-s-triazine-2,4-dithiol,-   6-[bis(2-hexyl)amino]-s-triazine-2,4-dithiol,-   6-diethylamino-s-triazine-2,4-dithiol,-   6-dicyclohexylamino-s-triazine-2,4-dithiol,-   6-diphenylamino-s-triazine-2,4-dithiol,-   6-dibenzylamino-s-triazine-2,4-dithiol,-   6-diallylamino-s-triazine-2,4-dithiol,-   6-didodecylamino-s-triazine-2,4-dithiol,-   6-dibutylamino-s-triazine-2,4-dithiol,-   6-dimethylamino-s-triazine-2,4-dithiol,-   6-phenylamino-s-triazine-2,4-dithiol,-   2-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine-2,4-dithiol,-   6-stearylamino-s-triazine-2,4-dithiol,-   6-ethylamino-s-triazine-2,4-dithiol,-   6-hexylamino-s-triazine-2,4-dithiol,-   6-(cis-9-octadecenylamino)-s-triazine-2,4-dithiol,-   6-cyclohexylamino-s-triazine-2,4-dithiol,-   6-(4-anilino-N-isopropylanilino)-s-triazine-2,4-dithiol,-   6-methoxy-s-triazine-2,4-dithiol,-   6-(1-naphthyloxy)-s-triazine-2,4-dithiol,-   6-(m-chlorophenoxy)-s-triazine-2,4-dithiol,-   6-(2,4-dimethylphenoxy)-s-triazine-2,4-dithiol, and-   6-phenoxy-s-triazine-2,4-dithiol.

Of these, 6-phenyl-2-triazine-2,4-dithiol is preferable.

Vinyl Ethers, etc.

Of the vinyl ethers, the aldehydes and the ketones employable for thepreparation of the thiol compound derivatives of the invention, vinylethers are preferably employed from the viewpoint of reactivity. Thevinyl ethers have only to contain at least one vinyl group per molecule,and monovinyl ethers, monovinyl thioethers and pyran derivatives orfuran derivatives which are cyclic vinyl ethers are available. Alsoavailable are polyvalent vinyl ethers, such as divinyl ethers, trivinylethers and tetravinyl ethers.

Of these, preferable are monovinyl ethers, monovinyl thioethers andpyran derivatives or furan derivatives which are cyclic vinyl ethers.

The vinyl ether is, for example, a vinyl ether or a vinyl thioetherrepresented by the following formula (20):

wherein R¹, R², R³ and A are the same as R¹, R², R³ and A in theaforesaid formula (2), and R¹ and R² may form a ring.

For the preparation of the thiol compound derivative of the invention,R¹ and R² in the formula (20) may form a ring. When R¹ and R² form aring, R¹ and R² are each preferably an alkyl group, and the alkyl groupmay have a substituent. In this case, R³ is preferably a hydrogen atom.

Examples of such vinyl ethers include the following compounds:

-   methyl-1-phenyl vinyl ether,-   ethyl-1-phenyl vinyl ether,-   methyl-1-methyl vinyl ether,-   ethyl-1-ethyl vinyl ether,-   ethyl-1-methyl vinyl ether,-   methyl vinyl ether,-   ethyl vinyl ether,-   propyl vinyl ether,-   isopropyl vinyl ether,-   n-butyl vinyl ether,-   isobutyl vinyl ether,-   sec-butyl vinyl ether,-   tert-butyl vinyl ether,-   pentyl vinyl ether,-   hexyl vinyl ether,-   heptyl vinyl ether,-   octyl vinyl ether,-   2-ethylhexyl vinyl ether,-   decyl vinyl ether,-   cetyl vinyl ether,-   stearyl vinyl ether,-   propadienyl vinyl ether,-   isopropenyl vinyl ether,-   2-propynyl vinyl ether,-   3-butynyl vinyl ether,-   3-methyl-2-butenyl vinyl ether,-   allyl vinyl ether,-   ethylene glycol monovinyl ether,-   diethylene glycol-monovinyl ether,-   triethylene glycol monovinyl ether,-   triethanolamine monovinyl ether,-   1-chloroethyl vinyl ether,-   2-chloroethyl vinyl ether,-   acetone oxime vinyl ether,-   2-methylallyl vinyl ether,-   3-phenylpropargyl vinyl ether,-   cyclohexyl vinyl ether,-   2-bromoethyl vinyl ether,-   methoxyethyl vinyl ether,-   2-butoxyethyl vinyl ether,-   diethylene glycol methyl vinyl ether,-   2-acetoxyethyl vinyl ether,-   dimethylaminoethyl vinyl ether,-   2-(diethylamino)ethyl vinyl ether,-   aminoethyl vinyl ether,-   3-dimethylaminopropyl vinyl ether,-   trimethylsiloxyethyl vinyl ether,-   trimethylsilyl vinyl ether,-   triethylsilyl vinyl ether,-   1-menthyl vinyl ether,-   2-methoxyphenyl vinyl ether,-   o-tolyl vinyl ether,-   p-nitrophenyl vinyl ether,-   2-naphthyl vinyl ether,-   phenyl vinyl ether,-   p-fluorophenyl vinyl ether,-   p-methoxyphenyl vinyl ether,-   p-aminophenyl vinyl ether,-   2,4,6-trichlorophenyl vinyl ether,-   2,4,6-trimethylphenyl vinyl ether,-   2,4-dichlorophenyl vinyl ether,-   2,4,6-tribromophenyl vinyl ether,-   N-methylaminophenyl vinyl ether,-   p-(dimethylamino)phenyl vinyl ether,-   4-acetylphenyl vinyl ether,-   2-nitrophenyl vinyl ether,-   3-nitrophenyl vinyl ether,-   p-iodophenyl vinyl ether,-   p-chlorophenyl vinyl ether,-   1-phenylethyl vinyl ether,-   benzyl vinyl ether, and-   2-piperidinoethyl vinyl ether,

Examples of the cyclic monovinyl ethers include:

-   2,3-dihydrofuran,-   3,4-dihydrofuran,-   2,3-dihydro-2H-pyran,-   3,4-dihydro-2H-pyran,-   3,4-dihydro-2-methoxy-2H-pyran,-   3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, and-   3,4-dihydro-2-ethoxy-2H-pyran.

The polyvalent vinyl ethers include divinyl ethers, trivinyl ethers andtetravinyl ethers.

Examples of the divinyl ethers include:

-   divinyl ether,-   divinyl formal,-   ethylene glycol divinyl ether,-   diethylene glycol divinyl ether,-   triethylene glycol divinyl ether,-   triethanolamine divinyl ether,-   1,3-propanediol divinyl ether,-   1,4-butanediol divinyl ether,-   1,4-cyclohexanediol divinyl ether,-   4,4′-dihydroxyazobenzene divinyl ether,-   hydroquinone divinyl ether, and-   bisphenol A divinyl ether.

Examples of the trivinyl ethers include glycerol trivinyl ether.

Examples of the tetravinyl ethers include pentaerythritol tetravinylether.

In the preparation using the polyvalent vinyl ether, the polyvalentvinyl ether is sometimes crosslinked with plural thiol compounds to forma high-molecular weight compound depending upon the preparationconditions.

The vinyl thioethers include vinyl thioethers corresponding to theaforesaid vinyl ethers and cyclic monovinyl ethers. Examples of suchvinyl thioethers include:

-   3-(trimethylsilyl)propyl vinyl thioether,-   2-hydroxyethyl vinyl thioether,-   2(N-morpholino) ethyl-5-vinyl thioether,-   2-(N-β-hydroxyethyl)aminoethyl-5-vinyl thioether,-   2-aminoethyl vinyl thioether,-   p-chlorophenyl vinyl thioether,-   phenyl vinyl thioether, and-   divinyl thioether.

Of these, particularly preferable is a thiol compound derivative whereinin the formula (20), A is an oxygen atom, R¹ is a hydrogen atom, R² isan alkyl group or a residue wherein a hydroxyl group is removed from(poly)alkylene glycol, and R³ is a hydrogen atom.

Catalyst

When the thiol compound derivative of the invention is prepared by thereaction of the thiol compound with a vinyl ether or the like, acatalyst can be used when needed. As the catalyst, an acid catalyst ispreferable, and examples of the acid catalysts employable herein includean acid phosphoric ester, hydrogen chloride, thionyl chloride and zincchloride. Of these, an acid phosphoric ester can be preferably employed.

The acid phosphoric ester is represented by, for example, the followingformula (21):

wherein R¹¹ is an alkyl group of 1 to 20 carbon atoms, a cycloalkylgroup or an allyl group, and m is 1 or 2.

The acid phosphoric ester is a phosphoric acid monoester or diester ofprimary alcohol or secondary alcohol. Examples of the primary alcoholsinclude 1-propanol, 1-butanol, 1-hexanol, 1-octanol and 2-ethylhexylalcohol. Examples of the secondary alcohols include 2-propanol,2-butanol, 2-hexanol, 2-octacnol and cyclohexanol.

The acid phosphoric esters can be used singly or in combination ofplural kinds.

When the acid phosphoric ester is used, the amount thereof is preferablyin the range of about 0.05 to 5% by weight. If the amount of the acidphosphoric ester is small, the reaction rate sometimes becomes slow.

Reaction Solvent

The reaction of the thiol compound with the vinyl ether or the like canbe carried out without a solvent or in a solvent. From the viewpoint ofreaction rate and workability, the reaction is preferably carried out ina solvent. As the solvent, any of publicly known organic solvents isemployable. For example, hydrocarbons, ethers, esters and ketones areemployable. Specifically, there can be mentioned benzene, toluene,xylene, ethylbenzene, dioxane, tetrahydrofuran, diethyl ether, dipropylether, methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate,acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone andmethyl propyl ketone.

Preparation of Thiol Compound Derivative

The thiol compound derivative of the invention can be obtained bycontacting the thiol compound with the vinyl ethers at a temperature ofpreferably room temperature to 180° C. in a solvent or without a solventand if necessary in the presence of an acid phosphoric ester. Thereaction time is usually in the range of about 1 to 60 minutes.

The thiol compound derivative of the invention is a compound wherein allor a part of hydrogen atoms of thiol groups of the thiol compound thatis a starting material are replaced with vinyl ethers or the like. Bycontrolling the compounding ratio between the thiol compound and thevinyl ethers, a desired thiol compound derivative can be obtained.Specifically, they have only to be reacted in, for example, thefollowing ratio.

When the trithiol compound (18) is used as a starting material and allof hydrogen atoms of three thiol groups (—SH) are replaced with a vinylether or the like to obtain the thiol compound derivative (1), the vinylether or the like is preferably used in an amount of 3 to 5 mol based on1 mol of the trithiol compound (18).

When the trithiol compound (18) is used as a starting material and twoof hydrogen atoms of three thiol groups (—SH) are replaced with a vinylether or the like to obtain the thiol compound derivative (8), the vinylether or the like is preferably used in an amount of 1.8 to 2.3 molbased on 1 mol of the trithiol compound (18).

When the thiol compound derivative (9) wherein a hydrogen atom of thethiol group is replaced with an alkali metal is obtained, 1.8 to 2.3 molof the vinyl ether or the like is reacted with a salt obtained byreacting the trithiol compound (18) with an aqueous solution of sodiumhydroxide or potassium hydroxide in an amount of 1 to 1.1 mol based on 1mol of the trithiol compound (18).

When the dithiol compound (19) is used as a starting material and all ofhydrogen atoms of two thiol groups (—SH) are replaced with a vinyl etheror the like to obtain the thiol compound derivative (10), the vinylether or the like is preferably used in an amount of 2 to 5 mol based on1 mol of the dithiol compound (19).

When the dithiol compound (19) is used as a starting material and one ofhydrogen atoms of two thiol groups (—SH) is replaced with a vinyl etheror the like to obtain the thiol compound derivative (15), the vinylether or the like is preferably used in an amount of 0.8 to 1.3 molbased on 1 mol of the dithiol compound (19).

When the thiol compound derivative (16) wherein a hydrogen atom of thethiol group is replaced with an alkali metal is obtained, 0.8 to 1.3 molof the vinyl ether or the like is reacted with a salt obtained byreacting the dithiol compound (19) with an aqueous solution of sodiumhydroxide or potassium hydroxide in an amount of 1 to 1.1 mol based on 1mol of the dithiol compound (19).

Treatment

If a catalyst having activity is contained in the thiol compoundderivative obtained, the thiol compound derivative sometimes undergoeshydrolysis depending upon the storage conditions, etc. Therefore, whenthe thiol compound derivative of the invention is prepared by thereaction of the thiol compound with the vinyl ethers in the presence ofan acid catalyst, it is preferable to remove or deactivate the catalystcontained in the reaction product. When the catalyst contained isremoved or deactivated, the thiol compound derivative is hardlydecomposed and is stable even if it is stored in the atmosphere for along period of time. Hence, the thiol compound derivative has excellentstorage properties and is more practical.

When the thiol compound derivative is obtained by contacting the thiolcompound with the vinyl ethers in the presence of an acid catalyst,particularly an acid phosphoric ester, it is desirable to treat thethiol compound derivative with hydrotalcite or metal alkoxide.

For the treatment using hydrotalcite, the reaction product containing anacid catalyst such as an acid phosphoric ester is contacted withhydrotalcite to allow the acid catalyst to be adsorbed on thehydrotalcite. The catalyst adsorbed on the hydrotalcide can be easilyremoved by, for example, filtration or precipitation.

In the treatment using metal alkoxide, the metal alkoxide is added tothe reaction product containing an acid catalyst such as an acidphosphoric ester to break an acid group of the acid catalyst (e.g.,phosphoric acid group of acid phosphoric ester) and thereby deactivatethe catalyst contained in the reaction product. The metal of the metalalkoxide used is preferably a metal selected from the group consistingof Ti, Al and Zr.

Uses of Thiol Compound Derivative

The thiol compound derivative of the invention is useful as acrosslinking agent and can be used by adding it to various curableresins. In the thiol compound derivative of the invention, the thiolgroup (—SH) is protected by a group derived from vinyl ether or thelike, so that when the thiol compound derivative is used as avulcanizing agent for acrylic rubbers, etc., excellent storage stabilityis exhibited, and for example, gelation of rubbers in the processingstage or the subsequent storing stage can be inhibited. Further, in thevulcanization molding or the crosslinking, the thiol compound having —SHgroup can be readily regenerated by eliminating the protective groupderived from the vinyl ether or the like by heating or other means.Therefore, the inherent reactivity can be easily restored to efficientlyperform vulcanization or crosslinking of a chlorine-containing acrylicrubber or a resin containing an epoxy group, and hence a crosslinkedproduct excellent in various properties can be obtained.

Elimination of the protective group derived from the vinyl ether or thelike is preferably carried out by the use of an acid catalyst. Examplesof the acid catalysts include halogenocarboxylic acid, sulfonic acid,sulfuric monoester, phosphoric monoester, phosphoric diester, boricmonoester and boric diester.

After regeneration of the thiol group, the thiol compound derivative ofthe invention can be used for the addition to a double bond, addition toan epoxy ring or substitution of organic chlorine.

The thiol compound derivative can be used singly, or can be used incombination with an accelerator, a dehalogenating agent or the like.

Examples of the rubbers or the resins having a double bond includenatural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber(SBR), butadiene rubber (BR), nitrile rubber (NBR), ethylene-propylenerubber (EPDM), unsaturated polyester resin, and acrylic rubber wherein adouble bond is introduced.

Example of the rubbers and the resins having an epoxy group includeepoxy resin oligomer and acrylic rubber containing an epoxy group.

Examples of the rubbers and the resins having organic chlorine includeacrylic rubber, chloroprene rubber (CR), epichlorohydrin rubber (CO,ECO), chlorinated polyethylene, and Polyvinyl chloride.

The thiol compound derivative of the invention can be used by mixing itwith one or more of the above rubbers or resins or adding it to amulti-layer structure of the above rubbers or resins.

The rubbers or the resins containing the thiol compound derivative ofthe invention are useful as materials for co-crosslinking molding orco-vulcanization molding, or they are vulcanization bonded to metals toform composite materials which are useful as molding materials.

Curable Composition

The curable composition of the invention contains the thiol compoundderivative.

The curable composition of the invention contains a halogen-containingcrosslinking polymer and the specific thiol compound derivative. Thehalogen-containing crosslinking polymer, the thiol compound derivativeand other components are described below.

Halogen-Containing Crosslinking Polymer

The halogen-containing crosslinking polymer for use in the invention isa high-molecular weight compound which contains halogen and iscrosslinkable. The halogen is a chlorine atom, a bromine atom or aniodine atom. Of these, a chlorine atom is preferable.

As the crosslinking polymer containing a chlorine atom,chlorine-containing acrylic rubber, epichlorohydrin rubber, chloroprenerubber, chlorosulfonated polyethylene or the like can be preferablyemployed. Of these, chlorine-containing acrylic rubber orepichlorohydrin rubber can be more preferably employed.

Halogen-Containing Acrylic Rubber

As the halogen-containing acrylic rubber, a copolymer of (A) at leastone acrylate type monomer selected from alkyl (meth)acarylates andalkoxyalkyl (meth)acrylates, (B) a crosslinking point monomer, and ifnecessary, (C) an ethylenically unsaturated monomer copolymerizable withthe acrylate type monomer can be preferably employed.

(A) Acrylate Type Monomer

The acrylate type monomer preferably employable is alkyl (meth)acrylateor akoxyalkyl (meth)acrylate.

As the alkyl (meth)acarylate, alkyl (meth)acrylate in which the numberof carbon atoms of the alkyl group is in the range of preferably 1 to15, more preferably 1 to 10, can be desirably employed. Examples of suchalkyl (meth)acrylates include acrylic esters and methacrylic esters,such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl(meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate,isobutyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate,2-ethylhexyl (meth)acrylate and n-octyl (meth)acrylate. These can beused singly or in combination of two or more kinds.

By the use of such alkyl (meth)acrylates, cured products havingexcellent low-temperature resistance and oil resistance can be obtained.A long alkyl chain is advantageous to the low-temperature resistance butis sometimes disadvantageous to the oil resistance. Contrary, a shortalkyl chain indicates a opposite tendency. Therefore, of the above alkyl(meth)acrylates, ethyl acrylate and butyl acrylate are particularlypreferable from the viewpoint of a balance between the oil resistanceand the low-temperature resistance.

As the alkoxyalkyl (meth)acarylate, alkoxyalkyl (meth)acrylate in whichthe number of carbon atoms of the alkyl group on the alkoxy group is inthe range of preferably 1 to 7, more preferably 1 to 4, and the numberof carbon atoms of the alkyl group bonded to an oxygen atom of acrylateis in the range of preferably 1 to 15, more preferably 1 to 10, can bedesirably employed. Examples of such alkoxyalkyl (meth)acrylates includemethoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, ethoxymethyl(meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl(meth)acrylate and 2- or 3-ethoxypropyl (meth)acrylate. These can beused singly or in combination of two or more kinds.

Of these, 2-methoxyethyl (meth)acrylate and 2-ethoxyethyl (meth)acrylateare more preferably employed.

By the use of such alkoxyalkyl (meth)acrylates, cured products havingexcellent low-temperature resistance and oil resistance can be obtained.

The alkyl (meth)acrylate and the alkoxyalkyl (meth)acrylate mentionedabove can be used independently or in combination. When the alkyl(meth)acrylate and the alkoxyalkyl (meth)acrylate are used incombination, the alkoxyalkyl (meth)acrylate is desirably used in anamount of preferably 10 to 40% by weight, more preferably 20 to 30% byweight, based on the alkyl (meth)acrylate. By the use of the alkyl(meth)acrylate and the alkoxyalkyl (meth)acrylate in such amounts, curedproducts excellent not only in low-temperature resistance and oilresistance but also in ordinary state properties such as heat resistancecan be obtained.

(B) Crosslinking Point Monomer

The crosslinking point monomer (B) used for preparing thehalogen-containing acrylic rubber for use in the invention is apolymerizable monomer having two or more functional groups and forms acrosslinking point of the halogen-containing acrylic rubber.

Examples of such bifunctional reactive monomers include a reactivehalogen-containing vinyl monomer, an epoxy group-containing vinylmonomer, a carboxyl group-containing vinyl monomer, a diene typemonomer, a hydroxyl group-containing monomer and an amidegroup-containing monomer.

Of these, at least one polymerizable monomer containing a reactivehalogen atom is used in the invention. That is to say, as thecrosslinking point monomer (B) for preparing the halogen-containingacrylic rubber for use in the invention, at least one reactivehalogen-containing monomer selected from the above bifunctional monomersis used, and further a bifunctional monomer containing no halogen atomselected from the above bifunctional monomers may be used incombination.

The halogen is chlorine, bromine or iodine, and preferable is chlorine.

Of the above bifunctional reactive monomers, the polymerizable monomerscontaining a halogen atom include reactive halogen-containing monomers,such as chloroethyl vinyl ether, chloroethyl acrylate, vinylbenzylchloride, vinyl chloroacetate, allyl chloroacetate andchloromethylstyrene.

When a combination of the reactive halogen-containing monomer and thebifunctional monomer containing no halogen atom is used as thecrosslinking point monomer, it is preferable to use a carboxylgroup-containing vinyl monomer of the above monomers.

Examples of the carboxyl group-containing vinyl monomers includemonocarboxylic acids, such as acrylic acid and methacrylic acid;dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid andcitraconic acid; and dicarboxylic monoesters, such as monomethylmaleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate,monoethyl fumarate and monobutyl fumarate. These carboxylgroup-containing vinyl monomers can be used singly or in combination oftwo or more kinds.

(C) Ethylenically Unsaturated Monomer

Examples of the ethylenically unsaturated monomers copolymerizable withthe acrylate type monomer (A) include styrene, vinyltoluene,α-methylstyrene, vinylnaphthalene, acrylonitrile, methacrylonitrile,acrylamide, cyclohexyl acrylate, phenyl (meth)acrylate, benzyl acrylate,vinyl acetate, ethyl vinyl ether, butyl vinyl ether, ethylene,piperylene, isoprene, pentadiene, butadiene, 2-hydroxyethyl acrylate and4-hydroxybutyl acrylate.

The above ethylenically unsaturated monomers (C) can be used singly orin combination of two or more kinds.

For the purpose of improving kneading processability, extrusionprocessability, etc., polyfunctional unsaturated monomers may be usedwhen needed. Specifically, oilgomers, e.g., di(meth)acrylates, such asethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate,1,6-hexanediol di(meth)acrylate and 1,9-nonanediol di(meth)acrylate;alkylene glyols, such as neopentyl glycol di(meth)acrylate,tetraethylene glycol di(meth)acrylate, tripropylene glycoldi(meth)acrylate and polypropylene glycol di(meth)acrylate; bisphenol A,EO adduct diacrylate, dimethyloltricyclodecane diacrylate, glycerolmethacrylate acrylate and 3-acryloyloxyglycerol monomethacrylate may beused.

From the viewpoint of a balance between the low-temperature resistance,the oil resistance and the heat resistance, it is desirable that in thehalogen-containing acrylic rubber for use in the invention, thecomponent derived from the acrylate type monomer (A) is contained in anamount of preferably 20 to 85% by weight, more preferably 30 to 70% byweight, the component derived from the reactive halogen-containingpolymerizable monomer as the crosslinking point monomer (B) is containedin an amount of preferably 0.1 to 15% by weight, more preferably 0.3 to5% by weight, and the component derived from the ethylenicallyunsataurated monomer (C) is contained in an amount of preferably 0 to79.9% by weight, more preferably 10 to 60% by weight, the total of saidcomponents (A), (B) and (C) being 100% by weight.

Although the molecular weight of the halogen-containing acrylic rubberis not specifically restricted, it is desirable that the weight-averagemolecular weight, as measured by gel permeation chromatography (GPC), ispreferably not more than 1000000, more preferably 50000 to 500000, fromthe viewpoints of processability and mechanical properties such asrubber strength.

Preparation of Halogen-Containing Acrylic Rubber

The halogen-containing acrylic rubber can be prepared by a publiclyknown process. For example, the acrylate type monomer (A) in an amountof preferably 20 to 85% by weight, more preferably 30 to 70% by weight,the reactive halogen-containing polymerizable monomer as thecrosslinking point monomer (B) in an amount of preferably 0.1 to 15% byweight, more preferably 0.3 to 5% by weight, and the ethylenicallyunsaturated monomer (C) in an amount of preferably 0 to 79.9% by weight,more preferably 10 to 60% by weight, the total of said components (A),(B) and (C) being 100% by weight, have only to be random polymerized inthe presence of a radical polymerization initiator through variousprocesses such as solution polymerization, bulk polymerization, emulsionpolymerization and suspension polymerization.

Epichlorohydrin Rubber

The epichlorohydrin rubber employable in the invention can be obtainedfrom a homopolymer of epichlorohydrin or by copolymerizingepichlorohydrin and alkylene oxide or unsaturated oxide.

The alkylene oxide preferably used is, for example, ethylene oxide orpropylene oxide. The unsaturated oxide is, for example, allyl glycidylether.

The epichlorohydrin rubber can be prepared by a publicly known process.Commercially available epichlorohydrin rubber is also employable.

As the copolymer of epichlorohydrin and alkylene oxide or unsaturatedoxide, a copolymer obtained by reacting epichlorohydrin with alkyleneoxide or the like in equimolar amounts is preferably employed, and acopolymer containing the component derived from the alkylene oxide orthe unsaturated oxide in an amount of preferably 10 to 90% by weight,more preferably 40 to 60% by weight, is desirable.

Although the molecular weight of the epichlorohydrin rubber is notspecifically restricted, it is desirable that the weight-averagemolecular weight, as measured by gel permeation chromatography (GPC), ispreferably not more than 200000, more preferably 5000 to 100000, fromthe viewpoints of processability and mechanical properties such asrubber strength.

Other Halogen-Containing Crosslinking Polymers

Examples of other halogen-containing crosslinking polymers employable inthe invention include chloroprene rubber, chlorosulfonated polyethylene,chlorinated polyethylene and Polyvinyl chloride. As such polymers,commercially available ones can be employed.

Thiol Compound Derivative

The curable composition of the invention, which contains thehalogen-containing crosslinking polymer, contains a thiol compoundderivative having at least one functional group represented by thefollowing formula (17) in one molecule.

wherein A, R¹, R² and R³ are the same as A, R¹, R² and R³ in theaforesaid formula (2).

The compound having a functional group represented by the formula (17)for use in the invention is, for example, a derivative of1,3,5-triazine-2,4,6-trithiol or 1,3,5-triazine-2,4-dithiol, and is acompound wherein the hydrogen atom of the thiol group (—SH) of the abovethiol compound is substituted with a specific substituent. The thiolcompound derivative can be obtained by reacting a compound having athiol group (—SH), such as triazinethiol, with vinyl ethers.

Examples of the thiol compound derivatives include the aforesaid thiolcompound derivatives of the invention, such as trithiol compoundderivatives, dithiol compound derivatives and monothiol compoundderivatives.

In addition to the above thiol compound derivatives, a thiol compoundderivative obtained by contacting the trithiol compound or the dithiolcompound with polyvalent vinyl ether is also available. The thiolcompound derivative obtained by the reaction with polyvalent vinyl etheris a polymer-like compound.

In the above case, the resulting thiol compound derivative is a compoundwherein all or a part of hydrogen atoms of thiol groups of triazinethiolthat is a starting material are replaced with the polyvalent vinylether, and in general, the polyvalent vinyl ether reacts with anothertriazinethiol to form a crosslinked structure.

The thiol compound derivative contained in the curable composition ofthe invention is a compound wherein all or a part of hydrogen atoms ofthiol groups of the thiol compound that is a starting material arereplaced with vinyl ethers or the like, and by controlling thecompounding ratio between the thiol compound and the vinyl ethers or thelike, a desired thiol compound derivative can be obtained.

When monovinyl ether is used as the vinyl ether, the thiol compoundderivative can be favorably obtained by the aforesaid process forpreparing the thiol compound derivative of the invention.

When polyvalent vinyl ether is used as the vinyl ether, the thiolcompound derivative can be obtained in the following manner.

The thiol compound represented by the aforesaid formula (18) or (19),namely, the thiol compound represented by the following formula (18) or(19) (wherein R⁵ is the same as that of aforesaid), is contacted withthe polyvalent vinyl ether to obtain a thiol compound derivative.

The thiol compound derivative thus obtained is a compound wherein all ora part of hydrogen atoms of thiol groups of the thiol compound that is astarting material are replaced with polyvalent vinyl ether, and ingeneral, the polyvalent vinyl ether reacts with another thiol compoundto form a crosslinked structure.

The compounding ratio between the thiol compound and the polyvalentvinyl ether usually varies depending upon the thiol compound and thepolyvalent vinyl ether used, so that preferred compounding ratios, etc.due to the type of the thiol compound are described below.

(i) Reaction of Trithiol Compound (18) with Polyvalent Vinyl Ether

(1) When the trithiol compound (18) is used as a starting material andall or a part of hydrogen atoms of three thiol groups (—SH) are replacedwith divinyl ether to obtain a thiol compound derivative, the divinylether is desirably used in an amount of preferably 1.5 to 20 mol, morepreferably 3 to 10 mol, based on 1 mol of the trithiol compound (18). Inthis case, though the divinyl ether may form a crosslinked structuretogether with the thiol compound, it is also possible that the divinylether does not form a crosslinked structure and a compound having afunctional group represented by the aforesaid formula (5) is produced.

It is presumed that the divinyl ether having reacted with the thiolcompound further reacts with another trithiol compound to form acrosslinked structure, as described above. More specifically, it ispresumed that the end vinyl group of the functional group representedby, for example, the aforesaid formula (5) reacts with another thiolcompound.

(2) When the trithiol compound (18) is used as a starting material andtrivinyl ether is used as the polyvalent-vinyl ether, the trivinyl etheris desirably used in an amount of preferably 1 to 15 mol, morepreferably 3 to 10 mol, based on 1 mol of the trithiol compound (18). Inthis case, similarly to the case of using the divinyl ether, it ispresumed that the trivinyl ether forms a crosslinked structure togetherwith the thiol compound. In the resulting product, a thiol compoundderivative wherein the trivinyl ether does not form a crosslinkedstructure may be present.

(3) When the trithiol compound (18) is used as a starting material andtetravinyl ether is used as the polyvalent vinyl ether, the tetravinylether is desirably used in an amount of preferably 0.75 to 10 mol, morepreferably 3 to 7 mol, based on 1 mol of the trithiol compound (18). Inthis case, similarly to the case of using the divinyl ether, it ispresumed that the tetravinyl ether forms a crosslinked structuretogether with the thiol compound. In the resulting product, a thiolcompound derivative wherein the tetravinyl ether does not form acrosslinked structure may be present.

The thiol compound derivative obtained from the trithiol compound (18)and the polyvalent vinyl ether as described above is a compositionhaving a crosslinked structure and having plural kinds of molecularweights, and is usually oligomer-like or polymer-like.

The viscosity of the thiol compound derivative is desired to be in therange of preferably 10 to 10000 cps, more preferably 1000 to 5000 cps.

The weight-average molecular weight of the thiol compound derivative isdesired to be in the range of preferably 400 to 10000, more preferably1000 to 5000.

(ii) Reaction of Dithiol Compound (19) with Polyvalent Vinyl Ether

(1) When the dithiol compound (19) is used as a starting material andall or a part of hydrogen atoms of two thiol groups (—SH) are replacedwith divinyl ether to obtain a thiol compound derivative, the divinylether is desirably used in an amount of preferably 1 to 20 mol, morepreferably 3 to 10 mol, based on 1 mol of the dithiol compound (19). Inthis case, though the divinyl ether may form a crosslinked structuretogether with the thiol compound, a thiol compound derivative whereinthe divinyl ether does not form a crosslinked structure may be produced.

(2) When the dithiol compound (19) is used as a starting material andtrivinyl ether is used as the polyvalent vinyl ether, the trivinyl etheris desirably used in an amount of preferably 0.7 to 10 mol, morepreferably 3 to 7 mol, based on 1 mol of the dithiol compound (19). Inthis case, similarly to the case of using the divinyl ether, it ispresumed that the trivinyl ether forms a crosslinked structure togetherwith the thiol compound. In the resulting product, a thiol compoundderivative wherein the trivinyl ether does not form a crosslinkedstructure may be present.

(3) When the dithiol compound (19) is used as a starting material andtetravinyl ether is used as the polyvalent vinyl ether, the tetravinylether is desirably used in an amount of preferably 0.5 to 7 mol, morepreferably 1 to 5 mol, based on 1 mol of the dithiol compound (19).

The thiol compound derivative obtained from the dithiol compound (19)and the polyvalent vinyl ether as described above is a compositionhaving a crosslinked structure and having plural kinds of molecularweights, and is usually oligomer-like or polymer-like.

The viscosity of the thiol compound derivative is desired to be in therange of preferably 10 to 10000 cps, more preferably 100 to 1000 cps.

The weight-average molecular weight of the thiol compound derivative isdesired to be in the range of preferably 400 to 10000, more preferably1000 to 5000.

Vulcanization Accelerator

In the present invention, in addition to the halogen-containingcrosslinking polymer and the thiol compound derivative, an organic acidmetal salt is preferably used as the vulcanization accelerator, and analkali metal salt of an organic carboxylic acid and/or an alkaline earthmetal salt of an organic carboxylic acid is more preferably used.

Examples of the alkali metal salts of organic carboxylic acidsemployable herein include lithium salts, potassium salts and sodiumsalts of organic carboxylic acids such as saturated fatty acids of 3 to18 carbon atoms, unsaturated fatty acids of 3 to 18 carbon atoms,aliphatic dicarboxylic acids and aromatic carboxylic acids. Morespecifically, there can be mentioned sodium stearate, potassiumstearate, sodium oleate, potassium oleate, sodium 2-ethylhexanoate,sodium tartrate, potassium tartrate, sodium propionate and sodiumacetate. Of these, potassium salts or sodium salts of fatty acids of 8to 18 carbon atoms are particularly preferable. The potassium saltsgenerally have a tendency to increase the vulcanizing rate as comparedwith the sodium salts.

Examples of the alkaline earth metal salts of organic carboxylic acidsemployable herein include magnesium salts, calcium salts, barium saltsand zinc salts of organic carboxylic acids such as saturated fatty acidsof 1 to 18 carbon atoms, unsaturated fatty acids of 3 to 18 carbonatoms, aliphatic dicarboxylic acids and aromatic carboxylic acids. Morespecifically, there can be mentioned magnesium stearate, calciumstearate, barium oleate, magnesium tartrate and calcium propionate. Ofthese, calcium salts or barium salts of fatty acids of 8 to 18 carbonatoms are particularly preferable.

Vulcanization Supplement Accelerator

The curable composition of the invention preferably contains avulcanization supplement accelerator together with the vulcanizationaccelerator. As the vulcanization supplement accelerator, a publiclyknown vulcanization supplement accelerator is employable. Examples ofsuch vulcanization supplement accelerators include oxides of metals suchas Mg, Ca, Ba, Zn, Na, K, Li, Fe and Cu, hydroxides, carbonates,dialkyldithiocarbamates, borates, phosphates, silicates, hydrotalcite,quaternary ammonium salt, phosphonium salt, polyethylene glycol,polyethylene glycol monoalkyl ether and polyethylene glycol dialkylether.

More specifically, there can be mentioned magnesium oxide, magnesiumhydroxide, barium hydroxide, magnesium carbonate, barium carbonate,calcium oxide, calcium hydroxide, calcium carbonate, calcium silicate,calcium phthalate, zinc oxide, tin oxide, lead oxide, zincdibutylthiocarbamate, barium metaborate, cetyl trimethylammonium bromideand polyethylene glycol #600. The metal oxides, the metal hydroxides andthe carbonates function as acid acceptors to increase the vulcanizationacceleration effect. For controlling the crosslinking reaction rate,vulcanization retarders (premature crosslinking inhibitors), such asN-(cyclohexylthio)phthalimide, sulfonamide derivatives and organicacids, may be used.

They can be used singly or in combination of plural kinds.

In the present invention, it is desirable to use, as the vulcanizationsupplement accelerator, an onium compound, such as an ammonium compound,a phosphonium compound, an arsonium compound, a stibonium compound, asulfonium compound, a selenonium compound, a stannonium compound or aniodonium compound.

Examples of the onium compounds preferably employable as thevulcanization supplement accelerator in the invention include quaternaryammonium compounds, such as methyltrioctylammonium chloride,laurylpyridinium chloride, tetraheptylammonium chloride,tetrabutylammonium stearate and cetylmethylammonium bromide; andquaternary phosphonium salts, such as methyltrioctylphosphoniumtetrafluoroborate, benzyltrioctylphosphonium bromide,benzyltrioctylphosphonium chloride, methyltrioctylphosphonium acetate,methyltrioctylphosphonium dimethyl phosphate andmethyltrioctylphosphonium chloride.

In the present invention, polyalkylene oxides such as polyethylene oxideand polypropylene oxide are also preferably used as the vulcanizationsupplement accelerator.

Anti-Aging Agent

It is also preferable that the curable composition of the inventioncontains an anti-aging agent in addition to the halogen-containingcrosslinking polymer and the thiol compound derivative. As theanti-aging agent, an anti-aging agent of amine type, quinoline type,phenol type, phosphite ester type or thioether type is preferablyemployed.

In an acrylic rubber composition, a diphenylamine type anti-aging agentsuch as 4,4-bis(α,α-dimethylbenzyl)diphenylamine is usually used singly,but in the present invention, it is desirable to use a diphenylaminetype anti-aging agent and a sulfur type anti-aging agent or a phosphorustype anti-aging agent in combination.

Preferred examples of the sulfur type anti-aging agents includethioether type compounds, such as dilauryl 3,3-thiodipropionate,distearyl 3,3-thiodipropionate and pentaerythritoltetrakis(3-laurylthiopropionate). Preferred examples of the phosphorustype anti-aging agents include phosphorous acid type compounds, such astris(nonylphenyl) phosphite.

Other Compounding Ingredients

The curable composition of the invention may further contain, ascompounding ingredients, additives other than the above-mentioned oneswithin limits not detrimental to the objects of the present invention.Examples of such compounding ingredients include a reinforcing agent, afiller, a plasticizer, a processing aid, a pigment, a lubricant and aresin other than the halogen-containing crosslinking polymer.

Curable Composition

The curable composition of the invention contains the halogen-containingcrosslinking polymer and the thiol compound derivative, and can furthercontain an organic acid metal salt, a vulcanization supplementaccelerator, an anti-aging agent, a reinforcing agent, a filler, aplasticizer, a pigment, a processing aid, a lubricant, etc., whenneeded.

The process for preparing the curable composition comprising thehalogen-containing crosslinking polymer and the thiol compoundderivative is not specifically restricted, and the composition can beprepared by a publicly known process. For example, the components areblended, kneaded by, for example, a roll or a closed kneader, and thenvulcanization molded under the crosslinking conditions publicly known.

The amount of the thiol compound derivative in the curable compositionis desired to be in the range of preferably 0.1 to 5% by weight, morepreferably 1 to 3% by weight, based on the halogen-containingcrosslinking polymer.

If the amount of the thiol compound derivative is less than 0.1% byweight, the crosslink density is sometimes decreased. If the amountthereof is more than 5% by weight, the crosslink density becomes so highthat the molded product sometimes becomes brittle.

The curable composition obtained can be crosslinked by heating. Thecrosslinking molding temperature is preferably in the range of about 130to 200° C. If the crosslinking temperature is lower than 130° C., thecomposition is not crosslinked or is insufficiently crosslinked in somecases. If the crosslinking temperature is higher than 200° C., thecrosslinking reaction proceeds so rapidly that the molding failure mayoccur.

The crosslinking time varies depending upon the crosslinking method,temperature or the shape and is not restricted, but usually, it is inthe range of 1 minute to 5 hours. The heating method is not specificallyrestricted, and heating can be carried out by means of press, steam,oven, hot air or the like.

The curable composition of the invention uses the specific compoundderivative as a crosslinking agent. That is to say, the thiol group(—SH) of the thiol compound derivative is protected by a group derivedfrom the vinyl ether or the like, so that when the thiol compoundderivative is used as a vulcanizing agent for a chlorine-containingacrylic rubber, etc., excellent storage stability is exhibited, and forexample, gelation of the rubber in the processing stage or thesubsequent storing stage can be inhibited. Further, in the vulcanizationmolding or the crosslinking molding, the protective group derived fromthe vinyl ether or the like can be eliminated by heating or other meansto easily regenerate the thiol compound having —SH group. Therefore, theinherent reactivity can be easily restored to efficiently performvulcanization or crosslinking of a chlorine-containing acrylic rubber ora resin containing an epoxy group, and as a result, a crosslinkedproduct excellent in various properties can be obtained.

Elimination of the protective group derived from the vinyl ether or thelike is preferably carried out by the use of an acid catalyst. Examplesof such acid catalysts include halogenocarboxylic acid, sulfonic acid,sulfuric monoester, phosphoric monoester, phosphoric diester, boricmonoester and boric diester.

After regeneration of the thiol group, the thiol compound derivative ofthe invention participates in the addition to a double bond, addition toan epoxy ring or substitution of organic chlorine. The thiol compoundderivative can be used singly, or can be used in combination with anaccelerator, a dehalogenating agent or the like.

The molded product obtained as above through crosslinking has excellenthardness, tensile strength and compression set, and is useful for hoses,sealing parts and the like.

The thiol compound derivative of the invention is useful as acrosslinking agent of a curable composition consisting of rubber, resin,etc., and a composition containing the thiol compound derivative of theinvention is excellent in storage stability before molding-cure becausethe reaction of the thiol compound is restrained. In the molding of thecomposition, the thiol compound having high reactivity can be easilyregenerated by heat, and hence, curing can be carried out rapidly at anytime. Further, by the use of the thiol compound derivative of theinvention as a vulcanizing agent of a curable composition, it becomesunnecessary to add a premature vulcanization inhibitor for controllingstorage properties or curability, which sometimes deteriorates variousproperties of a cured product. Hence, a cured product excellent invarious properties can be obtained.

Furthermore, because the thiol compound derivative in the curablecomposition of the invention is protected by a specific protective groupto thereby restrain the reaction, the curable composition exhibitsexcellent storage stability when stored before the molding-cure. In themolding of the curable composition, the thiol compound having highreactivity can be easily regenerated by heat, and hence, curing can becarried out rapidly at any time. By the use of the thiol compoundderivative of the invention as a vulcanizing agent of a curablecomposition, it becomes unnecessary to add a premature vulcanizationinhibitor for controlling storage properties or curability, whichsometimes deteriorates various properties of a cured product. Hence, acured product excellent in various properties can be obtained. Moreover,when the curable composition of the invention contains a specificvulcanization accelerator, a specific vulcanization supplementaccelerator and a specific anti-aging agent, the composition isexcellent in storage stability, crosslinking rate and physicalproperties of its crosslinked molded product with a better balance ofthose properties.

EXAMPLE

The present invention is further described with reference to thefollowing examples, but it should be construed that the invention is inno way limited to those examples.

In the following examples and comparative examples, IR measurements werecarried out by the use of FT/IR-7000 type Fourier transform infraredspectrophotometer (manufactured by Nippon Bunko Kogyo K.K.).

Example 1

In a four-necked flask equipped with a thermometer, a reflux condenserand a stirrer, 35.46 g (0.2 mol) of 1,3,5-triazine-2,4,6-trithiol, 0.3 gof acid butyl phosphate (AP-4, available from Daihachi Kagaku KogyoK.K.), 72.1 g (0.72 mol) of n-butyl vinyl ether and 190 g of acetonewere placed, and they were stirred and reacted at 70° C. until ahomogeneous solution was obtained. After the reaction was completed, thereaction solution was cooled and concentrated to obtain a yellow liquidcontaining crystals. The crystals were separated by filtration to obtain89.1 g of a viscous yellow liquid (thiol compound derivative A).

The viscous yellow liquid thus obtained was applied to a KRS-5 cell tomeasure an IR absorption spectrum. A chart of the measurement result isshown in FIG. 1. An IR absorption spectrum of1,3,5-triazine-2,4,6-trithiol which was a starting material was alsomeasured by the KBr tablet method. A chart of the measurement result isshown in FIG. 2.

As can be seen from FIG. 1, absorption at about 1619 cm⁻¹, that isabsorption by the double bond of n-butyl vinyl ether, disappears. As canbe seen from FIG. 1, further, absorption at about 1590 cm⁻¹, that isabsorption by the SH bond (enol structure) or the C═S bond (ketostructure) of the 1,3,5-triazine-2,4,6-trithiol and appears in FIG. 2,also disappears. From the results, it has been confirmed that theviscous yellow liquid A, which was the resulting product, was an adductof 1,3,5-triazine-2,4,6-trithiol with n-butyl vinyl ether, namely, athiol compound derivative of the following formula wherein the thiolgroup was added to the vinyl group. The yield of the product (thiolcompound derivative A) was 93% based on the1,3,5-triazine-2,4,6-trithiol.

Then, a part of the resulting viscous yellow liquid A was heated at atemperature of 180° C. for 5 minutes in the atmosphere. As a result, theliquid became a solid. When an IR absorption spectrum of the solid wasmeasured by the KBr tablet method, a result shown in FIG. 3 wasobtained. In the IR absorption spectrum of FIG. 3, there is absorptionat about 1590 cm⁻¹ assigned to the 1,3,5-triazine-2,4,6-trithiol whichwas a starting material, and it has been confirmed that the protectivegroup of the resulting compound represented by the aforesaid formula waseliminated by heat and the starting material compound was formed.

Example 2

A viscous yellow liquid (thiol compound derivative B) of 91.0 g wasobtained in the same manner as in Example 1, except that instead of 72.1g (0.72 mol) of n-butyl vinyl ether, isobutyl vinyl ether was used inthe same amount. The viscous yellow liquid thus obtained was applied toa KRS-5 cell to measure an IR absorption spectrum. A chart of themeasurement result is shown in FIG. 4.

As can be seen from FIG. 4, absorption at about 1621 cm⁻¹ assigned tothe double bond of isobutyl vinyl ether disappears. As can be seen fromFIG. 4, further, absorption at about 1590 cm⁻¹, that is assigned to theSH bond (enol structure) or the C═S bond (keto structure) of the1,3,5-triazine-2,4,6-trithiol and appears in FIG. 2, also disappears.From the results, it has been confirmed that the resulting product B wasan adduct of 1,3,5-triazine-2,4,6-trithiol with isobutyl vinyl ether,namely, a thiol compound derivative wherein the thiol group was added tothe vinyl group. The yield of the product (thiol compound derivative B)was 93% based on the 1,3,5-triazine-2,4,6-trithiol.

Then, a part of the resulting viscous yellow liquid B was heated at atemperature of 180° C. for 5 minutes in the atmosphere. As a result, theliquid became a solid. When an IR absorption spectrum of the solid wasmeasured by the KBr tablet method, a result shown in FIG. 5 wasobtained. In the IR absorption spectrum of FIG. 5, there is absorptionat about 1590 cm⁻¹ assigned to the 1,3,5-triazine-2,4,6-trithiol whichwas a starting material, and it has been confirmed that the protectivegroup of the resulting compound was eliminated by heat and the startingmaterial compound was formed.

Examples 3 to 7, Comparative Examples 1 to 5

The viscous yellow liquid A obtained in Example 1 and the viscous yellowliquid B obtained in Example 2 were each blended with the componentsshown in Table 7 in the proportions shown in Table 7 and kneaded by an8-inch open roll to prepare curable compositions.

As the Mooney scorch of the resulting curable compositions beforecuring, values immediately after blending and values after storage for 7days under the conditions of a temperature of 40° C. and a relativehumidity (RH) of 40% were measured by the method of JIS K 6300.

The curable compositions were heated at 180° C. for 8 minutes to performprimary vulcanization and then further heated at 175° C. for 4 hours toperform secondary vulcanization and thereby cured. The resulting curedproducts were measured on the hardness, tensile strength, elongation andcompression set. The secondary vulcanization products were furtherheated at 175° C. for 70 hours and then measured on the rate of changein hardness, rate of change in tensile strength and rate of change inelongation. Measurements of the properties were made in accordance withJIS K 6301. The results are set forth in Table 8.

Further, vulcanizing rates of the compositions obtained in the examplesand the comparative examples were measured by the use of acurelastometer V type (manufactured by Orientech K.K.). Thecurelastometer curves obtained are shown in FIG. 6. TABLE 7 Comp. Comp.Comp. Comp. Comp. Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 1 Ex. 2 Ex. 3 Ex. 4Ex. 5 Acrylic rubber 1 100 100 100 Acrylic rubber 2 100 100 100 Acrylicrubber 3 100 100 Epichlorohydrin 100 100 rubber Stearic acid 1 1 1 1 2 11 1 1 2 Diablack H 60 55 55 55 60 60 55 55 SEAST GSO 40 40 NOCRAC CD 2 22 2 2 2 2 2 2 2 TCY 0.7 0.7 0.4 0.6 0.9 TCYBVE 1.5 0.9 1.3 2.0 TCYIBVE0.9 NS Soap 3 3 3 3 3 3 3 3 MgO #150 1.5 1.5 PVI 1Notes:In the table, a unit for each numerical value is part by weight.Acrylic rubber 1: acrylic rubber obtained by polymerizing ethylacrylate, butyl acrylate, methoxyethyl acrylate and chloromethylstyrene(charge weight ratio = 50:20:30:1.5) by conventional procedureAcrylic rubber 2: acrylic rubber obtained by polymerizing ethylacrylate, butyl acrylate, methoxyethyl acrylate and vinyl chloroacetate(charge weight ratio = 40:40:50:2) by conventional procedureAcrylic rubber 3: acrylic rubber obtained by polymerizing ethylacrylate, butyl acrylate, methoxyethyl acrylate and chloroethyl vinylether (charge weight ratio = 50:20:30:5) by conventional procedureEpichlorohydrin rubber: Epichlomer C (available from Osaka Soda K.K.)Diablack H: available from Mitsubishi Chemical Corporation, HAF carbonblackSEAST GSO: available from Tokai Carbon K.K., FEF carbon blackNOCRAC CD: available from Ouchi Shiko Kagaku K.K., secondary amine typeanti-aging agentTCY: 1,3,5-triazine-2,4,6-trithiolTCYBVE: thiol compound derivative prepared in Example 1TCYIBVE: thiol compound derivative prepared in Example 2NS Soap: available from Kao Soap Co., Ltd., semi-hard beef tallow fattyacid sodaMgO #150: available from Kyowa Kagaku K.K., magnesium oxidePVI: available from Japan Monsant K.K., N-cyclohexylthiophthalimide(premature vulcanization inhibitor)

TABLE 8 Comp. Comp. Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Comp. Ex. 1 Comp. Ex.2 Comp. Ex. 3 Ex. 4 Ex. 5 Mooney scorch (125° C.) ML1 + 4 69 58 63 69 33impossible 100 impossible 62 57 t5 (min) 5.8 12.1 13.0 20.4 15.7impossible 2.9 impossible 10.4 10.8 Mooney scorch (125° C.) afterstorage of 40° C., 40% RH and 7 days ML1 + 4 53 46 40 34 48 unmeasuredimpossible unmeasured 38 92.5 t5 (min) 6.2 6.7 6.9 21.0 9.8 unmeasuredimpossible unmeasured 13.5 6.5 Properties after secondary vulcanizationHardness (JIS-A) 7.4 63 62 69 60 unmeasured 73 unmeasured 67 63 Tensile12.4 10.8 11.3 11.0 7.3 unmeasured 12.1 unmeasured 11.7 9.5 strength(MPa) Elongation (%) 160 220 240 220 360 unmeasured 190 unmeasured 210410 Compression set 13 11 10 12 26 unmeasured 19 unmeasured 17 32 (%)(150° C., 70 hrs) Properties after heating of secondary vulcanizationproduct Rate of change +3 +5 +7 +7 −23 unmeasured +5 unmeasured +6 −25in hardness (%) Rate of change −8 −4 +1 −6 −92 unmeasured −8 unmeasured−3 −95 in tensile strength (%) Rate of change +5 −18 4 −9 −56 unmeasured−5 unmeasured −10 −76 in elongation (%)Notes:In the table, the term “impossible” means that the measurement isimpossible.

When triazinetrithiol publicly known and the acrylic rubber 1 obtainedby copolymerization with chloromethylstyrne as a crosslinking group wereused (Comparative Example 1) or when triazinetrithiol publicly known andthe acrylic rubber 2 obtained by copolymerization with vinylchloroacetate as a crosslinking group were used (Comparative Example 3),curing proceeded so rapidly that the Mooney viscosity and the scorchtime could not be measured. Even if the premature vulcanizationinhibitor was added (Comparative Example 2), the Mooney scorch afterstorage for 7 days at 40° C. and 40% RH was immeasurable, and thelong-term storage stability was poor.

On the other hand, when the thiol compound derivative obtained inExample 1 or 2 and the acrylic rubber 1 obtained by copolymerizationwith chloromethylstyrene as a crosslinking group or the acrylic rubber 2obtained by copolymerization with vinyl chloroacetate as a crosslinkinggroup were used (Examples 3 to 5), the long-term stability and thecurability were both satisfactory, and besides, the properties wereexcellent.

When triazinetrithiol publicly known and the acrylic rubber 3 obtainedby copolymerization with chloroethyl vinyl ether as a crosslinking groupwere used (Comparative Example 4), the compression set was poorer ascompared with the case where the thiol compound derivative obtained inExample 1 and the acrylic rubber 3 were used (Example 6).

When triazinetrithiol publicly known and epichlorohydrin were used(Comparative Example 5), the storage properties, curability andcompression set were poorer as compared with the case where the thiolcompound derivative obtained in Example 1 and the epichlorohydrin rubberwere used (Example 7).

When curelastometer curves of the compositions of Examples 3 to 7 andComparative Examples 2, 4 and 5 at a crosslinking temperature of 180° C.were measured, results shown in FIG. 9 were obtained. Measurements ofthe curelastometer curves were made in accordance with JIS K 6300 usinga curelastometer V type (manufactured by Orientech K.K.). Themeasurements were made under the conditions of an amplitude of ±1° and afrequency of 100 cps. In FIG. 6, the curelastometer curves of thecompositions of Examples 3 to 7 and Comparative Examples 2, 4 and 5 areshown. TABLE 9 tc₁₀ tc₉₀ t_(Δ80) T₁₀ M_(L) M_(H) (min) (min) (min) (kg ·cm) (kg · cm) (kg · cm) Ex. 3 0.76 4.51 3.75 9.2 2.2 9.4 Ex. 4 0.85 4.603.75 7.7 2.0 7.8 Ex. 5 0.86 4.61 3.75 7.8 1.8 7.9 Ex. 6 1.92 8.25 6.338.3 1.9 8.8 Ex. 7 2.55 8.99 6.44 5.1 1.6 5.7 Comp. 0.58 5.28 4.70 8.32.3 8.5 Ex. 2 Comp. 1.83 8.41 6.58 7.3 2.2 7.8 Ex. 4 Comp. 2.37 8.976.60 6.3 2.1 6.9 Ex. 5tc₁₀ (min): time required for torque to reach 10% of (M_(H) − M_(L));this means an induction period (scorch time).tc₉₀ (min): time required for torque to reach 90% of (M_(H) − M_(L));this means the highest vulcanization point.t_(Δ80) (min): value of tc₉₀ − tc₁₀; this is a vulcanizing rate index ofa certain kind.T₁₀ (kg · cm): value of torque after 10 minutes from the beginning ofthe testM_(L) (kg · cm): minimum value of torqueM_(H) (kg · cm): maximum value of torque

Examples 8 to 33, Comparative Example 6

The viscous yellow liquid B obtained in Example 2, the acrylic rubber ofethyl acrylate/butyl acrylate/methoxyethyl acrylate/vinyl chloroacetate(40/40/20/2) and the components shown in Table 10, Table 11 and Table 12except the vulcanizing agent and the vulcanization accelerator werekneaded by a 3.6-liter Banbury mixer (manufactured by Kobe Steel, Ltd.),then the vulcanizing agent and the vulcanization accelerator were added,and they were kneaded by an open roll to prepare curable compositionsshown in Table 10, Table 11 and Table 12.

As the Mooney scorch of the resulting curable compositions beforecuring, values immediately after blending and values after storage for 7days under the conditions of a temperature of 40° C. and a relativehumidity (RH) of 40% were measured by the method of JIS K 6300.

The curable compositions were subjected to press vulcanization moldingat 180° C. for 8 minutes to perform primary vulcanization and thenfurther subjected to secondary vulcanization at 175° C. for 4 hours tocure them. Properties of the primary vulcanization products and thesecondary vulcanization products are set forth in Table 13, Table 14 andTable 15. TABLE 10 (Composition) Comp. Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12Ex. 13 Ex. 14 Ex. 15 Ex. 6 Acrylic rubber*1 100 100 100 100 100 100 100100 100 Stearic acid 1 1 1 1 1 1 1 1 14,4′-Bis(α,α-dimethylbenzyl)diphenylamine 2 2 2 2 2 2 2 2 MAF (N550)carbon 50 50 50 50 50 50 50 50 50 SRF (N774) carbon 35 35 35 35 35 35 3535 35 Thiol compound derivative B 1 1 1 1 1 1 1 1 Sodium stearate 3 3 33 3 Potassium stearate 3 Calcium stearate 3 Barium stearate 3 Magnesiumstearate 3 Zinc stearate 3 Aluminum stearate 32,4,6-Trimercapto-S-triazine 0.5 Zinc dibutyldithiocarbamate 2Notes:In the table, a unit for each numerical value is part by weight.Acrylic rubber*1: acrylic rubber of ethyl acrylate/butylacrylate/methoxyethyl acrylate/vinyl chloroacetate (40/40/20/2)

TABLE 11 (Composition) Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 Ex. 22Ex. 23 Ex. 24 Ex. 25 Acrylic rubber*¹ 100 100 100 100 100 100 100 100100 100 Stearic acid 1 1 1 1 1 1 1 1 1 1 4,4′-Bis(α,α- 2 2 2 2 2 2 2 2 2dimethylbenzyl)diphenylamine MAF (N550) carbon 50 50 50 50 50 50 50 5050 50 SRF (N774) carbon 35 35 35 35 35 35 35 35 35 35 Thiol compoundderivative B 1 1 1 1 1 1 1 1 1 1 Sodium stearate 3 3 3 3 3 3 3 3 3 3Cetylmethylammonium bromide 0.005 0.05 0.5 Magnesium oxide 2 Calciumhydroxide 2 Calcium carbonate 2 Zinc oxide 2 Lead oxide 2 HydrotalciteDHT-4A 2Notes:In the table, a unit for each numerical value is part by weight.Acrylic rubber*¹: acrylic rubber of ethyl acrylate/butylacrylate/methoxyethyl acrylate/vinyl chloroacetate (40/40/20/2)

TABLE 12 (Composition) Ex. 26 Ex. 27, Ex. 28 Ex. 29 Ex. 30 Ex. 31 Ex. 32Ex. 33 Acrylic rubber*¹ 100 100 100 100 100 100 100 100 Stearic acid 1 11 1 1 1 1 1 4,4′-Bis(α,α-dimethylbenzyl)diphenylamine 2 2 2 2 2 2 2 MAF(N550) carbon 50 50 50 50 50 50 50 50 SRF (N774) carbon 35 35 35 35 3535 35 35 Thiol compound derivative B 1 1 1 1 1 1 1 1 Sodium stearate 3 33 3 3 3 3 3 NOCRAC CD*² 2 2 2 NOCRAC 400*³ 2 NOCRAC TNP*⁴ 2 NOCRAC MB*⁵2 NOCRAC NEC*⁶ 2 NOCRAC NS-10-N*⁷ 2Notes:In the table, a unit for each numerical value is part by weight.*¹Acrylic rubber: acrylic rubber of ethyl acrylate/butylacrylate/methoxyethyl acrylate/vinyl chloroacetate (40/40/20/2)*NOCRAC: available from Ouchi Shinko Kagaku Kogyo K.K., anti-aging agent*²NOCRAC CD: amine type anti-aging agent(4,4′-bis(α,α-dimethylbenzyl)diphenylamine)*³NOCRAC 400: thioether type anti-aging agent (dilauryl thiopropionate)*⁴NOCRAC TNP: phosphorus type anti-aging agent (tri(nonylphenyl)phosphite)*⁵NOCRAC MB: imidazole type anti-aging agent (2-mercaptobenzoimidazole)*⁶NOCRAC NEC: carbamate type anti-aging agent (nickeldiethyldithiocarbamate)*⁷NOCRAC NS-10-N: thiourea type anti-aging agent(1,3-bis(dimethylaminopropyl)-2-thiourea)

TABLE 13 (Properties) Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex.15, Comp. Ex. 6 Properties in unvulcanized state (stability) Mooneyscorch 125° C. (initial value) ML1 + 4 51 60 51 52 51 48 50 48 62 t5(min) 5.9 5.9 10.1 10.6 15.3 >30 >30 >30 5.2 Mooney scorch 125° C.(after storage of 40° C., 40% RH and 7 days) ML1 + 4 48 71 49 47 45immeasurable t5 (min) 5.5 4.9 7.7 7.6 10.7 immeasurable Properties afterprimary vulcanization (primary vulcanization conditions. 180° C./8 min)Hardness (Pts) (JIS K 66 64 60 68 — — — 6253) Tensile strength (MPa) 8.08.7 6.9 7.5 — — — (JIS K 6251) Elongation at break (%) 250 240 540 300 —— — (JIS K 6251) Compression set (JIS K 22 17 73 30 — — — 6262) 25%compression, 150° C./70 hrs Properties after secondary vulcanization(primary vulcanization conditions: 180° C./8 min, secondaryvulcanization conditions: 170° C./4 hrs) Hardness (Pts) (JIS K 69 66 6870 69 — — — 64 6253) Tensile strength (MPa) 9.4 10.0 9.5 9.1 7.6 — — —10.1 (JIS K 6251) Elongation at break (%) 210 190 310 230 370 — — — 220(JIS K 6251) Compression set (JIS K 12 10 31 15 42 — — — 11 6262) 25%compression, 150° C./70 hrsNotes:In Examples 13, 14 and 15, vulcanization reaction did not proceed underthe above conditions, and vulcanization molding of the composition wasimpossible

TABLE 14 (Properties) Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 Ex. 22Ex. 23 Ex. 24 Ex. 25 Properties in unvulcanized state (stability) Mooneyscorch 125° C. (initial value) ML1 + 4 48 54 51 62 61 49 55 56 47 t5(min) 5.7 4.7 5.9 4.8 5.6 7.8 6.3 7.4 9.0 Mooney scorch 125° C. (afterstorage of 40° C., 40% RH and 7 days) ML1 + 4 44 55 48 74 86 47 74 72 41t5 (min) 5.1 4.0 5.5 5.2 4.1 6.8 5.6 4.9 8.9 Properties after primaryvulcanization (primary vulcanization conditions: 180° C./8 min) Hardness(Pts) (JIS K 65 65 66 66 71 71 67 69 56 70 6253) Tensile strength (MPa)7.8 8.1 9.3 8.0 8.1 8.0 7.8 7.5 5.9 8.2 (JIS K 6251) Elongation at break(%) 250 230 150 250 260 230 250 290 580 240 (JIS K 6251) Compression set(JIS K 22 21 14 22 51 39 24 38 82 38 6262) 25% compression, 150° C./70hrs Properties after secondary vulcanization (primary vulcanizationconditions: 180° C./8 min, secondary vulcanization conditions: 170° C./4hrs) Hardness (Pts) (JIS K 68 68 68 69 75 73 69 72 60 70 6253) Tensilestrength (MPa) 9.5 10.0 10.1 9.4 9.6 9.6 9.1 8.5 7.9 9.5 (JIS K 6251)Elongation at break (%) 190 180 160 210 200 200 200 230 370 220 (JIS K6251) Compression set (JIS K 12 13 10 12 36 25 14 31 40 25 6262) 25%compression, 150° C./70 hrs

TABLE 15 (Properties) Ex. 26 Ex. 27 Ex. 28 Ex. 29 Ex. 30 Ex. 31 Ex. 32Ex. 33 Properties in unvulcanized state (stability) Mooney scorch 125°C. (initial value) ML1 + 4 41 40 39 42 42 45 44 53 t5 (min) 9.7 6.5 10.210.7 5.2 3.6 10.2 2.3 Mooney scorch 125° C. (after storage of 40° C.,40% RH and 7 days) ML1 + 4 43 41 40 42 44 46 43 55 t5 (min) 9.2 6.4 10.09.9 4.8 3.7 9.8 2.1 Properties after primary vulcanization (primaryvulcanization conditions: 180° C./8 min) Hardness (Pts) (JIS K 64 63 6464 63 59 68 67 6253) Tensile strength (MPa) 8.6 8.3 8.5 8.4 8.5 9.0 8.69.6 (JIS K 6251) Elongation at break (%) 200 240 220 220 240 310 210 210(JIS K 6251) Compression set (JIS K 19 20 28 30 29 61 32 30 6262) 25%compression, 150° C./70 hrs Properties after secondary vulcanization(primary vulcanization conditions: 180° C./8 min, secondaryvulcanization conditions: 170° C./4 hrs) Hardness (Pts) (JIS K 70 69 6970 69 67 71 74 6253) Tensile strength (MPa) 10.3 10.1 10.2 10.6 10.910.7 10.1 12.2 (JIS K 6251) Elongation at break (%) 180 190 180 180 190230 180 140 (JIS K 6251) Compression set (JIS K 12 13 13 14 15 18 19 256262) 25% compression, 150° C./70 hrs

As can be seen from Table 10 and Table 13, of the compositionscontaining the acrylic rubber (halogen-containing crosslinking polymer)and the specific thiol compound derivative, the compositions containingan organic acid alkali metal salt or an organic acid alkaline earthmetal salt as the vulcanization accelerator readily underwentvulcanization reaction even in the case where the vulcanization moldingwas carried out under the same conditions, and the vulcanization moldedproducts had excellent properties.

As can be seen from Table 11 and Table 14, when an organic acid metalsalt was contained as the vulcanization accelerator and an oniumcompound was contained as the vulcanization supplement accelerator, eventhe primary vulcanization products showed excellent compression set alsoin the case where the vulcanization molding was carried out under thesame conditions.

As can be seen from Table 12 and Table 15, when an amine type compound,a sulfur compound of thioether type or a phosphorus compound ofphosphite type was used as the anti-aging agent, aging could beprevented. Moreover, the vulcanization products had excellent physicalproperties, and in particular, even the primary vulcanization productsshowed excellent compression set.

Example 34

In a four-necked flask equipped with a thermometer, a reflux condenserand a stirrer, 19.5 g (0.11 mol) of 1,3,5-triazine-2,4,6-trithiol, 200 gof acetone, 88.8 g (0.3 mol) of octadecyl vinyl ether and 0.3 g ofacidic butyl phosphate ester (AP-4, available from Daihachi Kagaku KogyoK.K.) were placed, and they were reacted at 65° C. for 16 hours. To thereaction solution, 200 g of toluene was added, and the insolubles werefiltered. Then, the filtrate was concentrated to obtain 99.23 g of alight yellow waxy substance.

The waxy substance thus obtained was applied to a KRS-5 cell to measurean IR absorption spectrum. A chart of the measurement result is shown inFIG. 7.

As can be seen from FIG. 7, absorption at about 1620 cm⁻¹, that isabsorption by the double bond of octadecyl vinyl ether, disappears. Ascan be seen from FIG. 7, further, absorption at about 1590 cm⁻¹, that isabsorption by the SH bond (enol structure) or the C═S bond (ketostructure) of the 1,3,5-triazine-2,4,6-trithiol and appears in FIG. 2,also disappears. From the results, it has been confirmed that the waxysubstance, which was the resulting product, was an adduct of1,3,5-triazine-2,4,6-trithiol with octadecyl vinyl ether, namely, athiol compound derivative wherein the thiol group was added to the vinylgroup. The yield of the product was 93% based on the octadecyl vinylether.

Example 35

In a four-necked flask equipped with a thermometer, a reflux condenserand a stirrer, 45 g (0.17 mol) of 6-dibutylamino-5-triazine-2,4-dithiol,200 g of acetone, 36.6 g (0.367 mol) of n-butyl vinyl ether and 0.3 g ofacid butyl phosphate (AP-4, available from Daihachi Kagaku Kogyo K.K.)were placed, and they were reacted at 60° C. for 12 hours. The reactionsolution was concentrated to obtain 74.05 g of a white paste.

The paste thus obtained was applied to a KRS-5 cell to measure an IRabsorption spectrum. A chart of the measurement result is shown in FIG.8. An IR absorption spectrum of 6-dibutylamino-5-triazine-2,4-dithiolwhich was a starting material was also measured by the KBr tabletmethod. A chart of the measurement result is shown in FIG. 9.

As can be seen from FIG. 8, absorption at about 1619 cm⁻¹, that isabsorption by the double bond of n-butyl vinyl ether, disappears. As canbe seen from FIG. 8, further, absorption at about 1600 cm⁻¹, that isabsorption by the SH bond (enol structure) or the C═S bond (ketostructure) of the 6-dibutylamino-5-triazine-2,4-dithiol and appears inFIG. 9, also disappears. From the results, it has been confirmed thatthe paste, which was the resulting product, was an adduct of6-dibutylamino-S-triazine-2,4-dithiol with n-butyl vinyl ether, namely,a thiol compound derivative wherein the thiol group was added to thevinyl group. The yield of the product was 95% based on the6-dibutylamino-S-triazine-2,4-dithiol.

Example 36

A viscous yellow liquid of 79.9 g was obtained in the same manner as inExample 34, except that 61.9 g (0.72 mol) of isopropyl vinyl ether wasused instead of 72.1 g (0.72 mol) of n-butyl vinyl ether.

The viscous yellow liquid thus obtained was applied to a KRS-5 cell tomeasure an IR absorption spectrum. A chart of the measurement result isshown in FIG. 10.

As can be seen from FIG. 10, absorption at about 1620 cm⁻¹, that isabsorption by the double bond of isopropyl vinyl ether, disappears. Ascan be seen from FIG. 10, further, absorption at about 1590 cm⁻¹, thatis absorption by the SH bond (enol structure) or the C═S bond (ketostructure) of the 1,3,5-triazine-2,4,6-trithiol and appears in FIG. 2,also disappears. From the results, it has been confirmed that theviscous yellow liquid, which was the resulting product, was an adduct of1,3,5-triazine-2,4,6-trithiol with isopropyl vinyl ether, namely, athiol compound derivative wherein the thiol group was added to the vinylgroup. The yield of the product was 92% based on the1,3,5-triazine-2,4,6-trithiol.

Example 37

A viscous yellow liquid of 85.9 g was obtained in the same manner as inExample 34, except that 68.0 g (0.54 mol) of cyclohexyl vinyl ether wasused instead of 72.1 g (0.72 mol) of n-butyl vinyl ether.

The viscous yellow liquid thus obtained was applied to a KRS-5 cell tomeasure an IR absorption spectrum. A chart of the measurement result isshown in FIG. 11.

As can be seen from FIG. 11, absorption at about 1620 cm⁻¹; that isabsorption by the double bond of cyclohexyl vinyl ether, disappears. Ascan be seen from FIG. 11, further, absorption at about 1590 cm⁻¹, thatis absorption by the SH bond (enol structure) or the C═S bond (ketostructure) of the 1,3,5-triazine-2,4,6-trithiol and appears in FIG. 2,also disappears. From the results, it has been confirmed that theviscous yellow liquid, which was the resulting product, was an adduct of1,3,5-triazine-2,4,6-trithiol with cyclohexyl vinyl ether, namely, athiol compound derivative wherein the thiol group was added to the vinylgroup. The yield of the product was 86% based on the cyclohexyl vinylether.

Example 38

A viscous yellow liquid of 40.2 g was obtained in the same manner as inExample 34, except that 68.0 g (0.59 mol) of 4-hydroxybutyl vinyl etherwas used instead of 72.1 g (0.72 mol) of n-butyl vinyl ether.

The viscous yellow liquid thus obtained was applied to a KRS-5 cell tomeasure an IR absorption spectrum. A chart of the measurement result isshown in FIG. 12.

As can be seen from FIG. 12, absorption at about 1620 cm⁻¹, that isabsorption by the double bond of 4-hydroxybutyl vinyl ether, disappears.As can be seen from FIG. 12, further, absorption at about 1590 cm⁻¹,that is absorption by the SH bond (enol structure) or the C═S bond (ketostructure) of the 1,3,5-triazine-2,4,6-trithiol and appears in FIG. 2,also disappears. From the results, it has been confirmed that theviscous yellow liquid, which was the resulting product, was an adduct of1,3,5-triazine-2,4,6-trithiol with 4-hydroxybutyl vinyl ether, namely, athiol compound derivative wherein the thiol group was added to the vinylgroup. The yield of the product was 39% based on the 4-hydroxybutylvinyl ether.

Example 39

In a four-necked flask equipped with a thermometer, a reflux condenserand a stirrer, 35.46 g (0.2 mol) of 1,3,5-triazine-2,4,6-trithiol, 0.3 gof acid butyl phosphate (AP-4, available from Daihachi Kagaku KogyoK.K.), 72.1 g (0.72 mol) of isobutyl vinyl ether and 190 g of acetonewere placed, and they were reacted at 65° C. for 0.16 hours. After thereaction was completed, the insolubles were filtered, and the filtratewas concentrated to obtain 91 g of a viscous yellow liquid.

The viscous yellow liquid thus obtained was applied to a KRS-5 cell tomeasure an IR absorption spectrum. A chart of the measurement result isshown in FIG. 13.

As can be seen from FIG. 13, absorption at about 1621 cm⁻¹, that isabsorption by the double bond of isobutyl vinyl ether, disappears. Ascan be seen from FIG. 13, further, absorption at about 1590 cm⁻¹, thatis absorption by the SH bond (enol structure) or the C═S bond (ketostructure) of the 1,3,5-triazine-2,4,6-trithiol and appears in FIG. 2,also disappears. From the results, it has been confirmed that theresulting product was an adduct of 1,3,5-triazine-2,4,6-trithiol withisobutyl vinyl ether, namely, a thiol compound derivative wherein thethiol group was added to the vinyl group. The yield of the product was93% based on the 1,3,5-triazine-2,4,6-trithiol.

The viscous yellow liquid, which was the resulting product, was appliedin a thickness of about 1 mm to a slide glass and allowed to stand for70 days in the atmosphere at a temperature of 23±2° C. and a humidity of50±5%. As a result, the liquid became a solid. When an IR absorptionspectrum of the yellow solid was measured by the KBr tablet method usingthe aforesaid infrared spectrophotometer, a result shown in FIG. 14 wasobtained. As can be seen from FIG. 14, there is absorption at about 1590cm⁻¹ assigned to the 1,3,5-triazine-2,4,6-trithiol which was a startingmaterial, and it was proved that the product had been decomposed.

Example 40

In a four-necked flask equipped with a thermometer, a reflux condenserand a stirrer, 35.46 g (0.2 mol) of 1,3,5-triazine-2,4,6-trithiol, 0.3 gof acid butyl phosphate (AP-4, available from Daihachi Kagaku KogyoK.K.), 72.1 g (0.72 mol) of isobutyl vinyl ether and 190 g of acetonewere placed, and they were reacted at 65° C. for 16 hours. After thereaction was completed, 4.0 g of hydrotalcite (Kyoward 500SH, availablefrom Kyowa Kagaku Kogyo K.K.) was added, and they were stirred at 40° C.for 10 hours. Then, the mixture was filtered, and the filtrate wasconcentrated to obtain 80 g of a viscous yellow liquid.

The viscous yellow liquid thus obtained was applied to a KRS-5 cell tomeasure an IR absorption spectrum. A chart of the measurement result isshown in FIG. 15.

As can be seen from FIG. 15, absorption at about 1621 cm⁻¹, that isabsorption by the double bond of isobutyl vinyl ether, disappears. Ascan be seen from FIG. 15, further, absorption at about 1590 cm⁻¹, thatis absorption by the SH bond (enol structure) or the C═S bond (ketostructure) of the 1,3,5-triazine-2,4,6-trithiol and appears in FIG. 2,also disappears. From the results, it has been confirmed that theresulting product was an adduct of 1,3,5-triazine-2,4,6-trithiol withisobutyl vinyl ether, namely, a thiol compound derivative wherein thethiol group was added to the vinyl group. The yield of the product was84% based on the 1,3,5-triazine-2,4,6-trithiol.

The viscous yellow liquid, which was the resulting product, was appliedin a thickness of about 1 mm to a slide glass and allowed to stand for70 days in the atmosphere at a temperature of 23±2° C. and a humidity of50±5%. As a result, there was no change of appearance such as turbidity.When the viscous yellow liquid having been allowed to stand for 70 dayswas applied to a KRS-cell to measure an IR absorption spectrum, a resultshown in FIG. 16 was obtained. As can be seen from FIG. 16, there is noabsorption at about 1590 cm⁻¹ assigned to the1,3,5-triazine-2,4,6-trithiol which was a starting material, anddecomposition of the product was not confirmed.

Example 41

In a four-necked flask equipped with a thermometer, a reflux condenserand a stirrer, 35.46 g (0.2 mol) of 1,3,5-triazine-2,4,6-trithiol, 0.3 gof acid butyl phosphate (AP-4, available from Daihachi Kagaku KogyoK.K.), 72.1 g (0.72 mol) of isobutyl vinyl ether and 190 g of acetonewere placed, and they were reacted at 65° C. for 16 hours. After thereaction was completed, 1.0 g of tetra(2-ethylhexyl) titanate (OrgaticsTA-30, available from Matsumoto Seiyaku Kogyo K.K.) was added, and themixture was concentrated to obtain 90 g of a viscous brown liquid.

The viscous brown liquid thus obtained was applied to a KRS-5 cell tomeasure an IR absorption spectrum. A chart of the measurement result isshown in FIG. 17.

As can be seen from FIG. 17, absorption at about 1621 cm⁻¹, that isabsorption by the double bond of isobutyl vinyl ether, disappears. Ascan be seen from FIG. 17, further, absorption at about 1590 cm⁻¹, thatis absorption by the SH bond (enol structure) or the C═S bond (ketostructure) of the 1,3,5-triazine-2,4,6-trithiol and appears in FIG. 2,also disappears. From the results, it has been confirmed that theresulting product was an adduct of 1,3,5-triazine-2,4,6-trithiol withisobutyl vinyl ether, namely, a thiol compound derivative wherein thethiol group was added to the vinyl group. The yield of the product was93% based on the 1,3,5-triazine-2,4,6-trithiol.

The viscous brown liquid, which was the resulting product, was appliedin a thickness of about 1 mm to a slide glass and allowed to stand for70 days in the atmosphere at a temperature of 23±2° C. and a humidity of50±5%. As a result, the viscous brown liquid had no change of appearancesuch as turbidity. When the viscous brown liquid having been allowed tostand for 70 days was applied to a KRS-cell to measure an IR absorptionspectrum, a result shown in FIG. 18 was obtained. As can be seen fromFIG. 18, there is no absorption at about 1590 cm⁻¹ assigned to the1,3,5-triazine-2,4,6-trithiol which was a starting material, anddecomposition of the product was not confirmed.

1-21. (canceled)
 22. A curable composition containing a compoundobtained by contacting triazinethiol with a polyvalent vinyl ether, anda halogen-containing crosslinking polymer.
 23. The curable compositionas claimed in claim 22, wherein the triazinethiol is represented by thefollowing formula (18):


24. The curable composition as claimed in claim 22, wherein thetriazinethiol is represented by the following formula (19):

wherein R⁵ is the same as R⁵ in the formula (10).
 25. The curablecomposition as claimed in claim 22, wherein the polyvalent vinyl etheris at least one ether selected from divinyl ethers, trivinyl ethers andtetravinyl ethers. 26-35. (canceled)